Co-reporter:Bing Zhang, Huai-Wei Wang, Yan-Shang Kang, Ping Zhang, Hua-Jin Xu, Yi Lu, and Wei-Yin Sun
Organic Letters November 3, 2017 Volume 19(Issue 21) pp:5940-5940
Publication Date(Web):October 19, 2017
DOI:10.1021/acs.orglett.7b02931
A general method for selective ortho C–H arylation of ketone, with boron reagent enabled by rhodium complexes with excellent yields, is developed. The transformation is characterized by the use of air-stable Rh catalyst, high monoarylation selectivity, and excellent yields of most of the substrates.
Co-reporter:Pei-Pei Cui, Xiu-Du Zhang, Peng Wang, Yue Zhao, Mohammad Azam, Saud I Al-Resayes, and Wei-Yin Sun
Inorganic Chemistry November 20, 2017 Volume 56(Issue 22) pp:14157-14157
Publication Date(Web):November 1, 2017
DOI:10.1021/acs.inorgchem.7b02235
The fabrication of metal–organic frameworks with controlled structure and desired properties is important but still a challenge. In this work, a zinc(II) framework, {[Zn3(L)2(DABCO)(H2O)]·9DMF} (named as Zn-1), has been synthesized based on [1,1′:3′,1″-terphenyl]-4,4″,5′-tricarboxylic acid (H3L) and 1,4-diazabicyclo[2.2.2]octane (DABCO), which is isostructural to the previously reported copper(II) analogue, {[Cu3(L)2(DABCO)(H2O)]·15H2O·9DMF} (named as Cu-1). Interestingly, hybrid zinc(II) and copper(II) bimetallic frameworks have been obtained via metal-ion metathesis and found to show enhanced adsorption and photoluminescence properties. Such a post-metal-ion metathesis method can be used to synthesize new and desired frameworks that could not be obtained by direct synthesis.
Co-reporter:Hua-Jin Xu, Yi Lu, Marcus E. Farmer, Huai-Wei Wang, Dan Zhao, Yan-Shang Kang, Wei-Yin Sun, and Jin-Quan Yu
Journal of the American Chemical Society February 15, 2017 Volume 139(Issue 6) pp:2200-2200
Publication Date(Web):January 27, 2017
DOI:10.1021/jacs.6b13269
A range of Rh(III)-catalyzed ortho-C–H functionalizations have been developed; however, extension of this reactivity to remote C–H functionalizations through large-ring rhodacyclic intermediates has yet to be demonstrated. Herein we report the first example of the use of a U-shaped nitrile template to direct Rh(III)-catalyzed remote meta-C–H activation via a postulated 12-membered macrocyclic intermediate. Because the ligands used for Rh(III) catalysts are significantly different from those of Pd(II) catalysts, this offers new opportunities for future development of ligand-promoted meta-C–H activation reactions.
Co-reporter:Yu-Ling Li;Yue Zhao;Yan-Shang Kang;Xiao-Hui Liu
Crystal Growth & Design December 7, 2016 Volume 16(Issue 12) pp:7112-7123
Publication Date(Web):November 11, 2016
DOI:10.1021/acs.cgd.6b01352
Seven new frameworks [Co3(tib)2(BPT)2(H2O)2]·DMA·2.5H2O (1), [Co3(tib)2(BPT)2(H2O)2]·DMF·3H2O (2), [Ni3(tib)2(BPT)2(H2O)2]·DMF·1.5H2O (3), [Ni3(tib)2(BPT)2(H2O)6]·2H2O (4), [Mn(tib)(H2O)3]·HBPT·DMF·2H2O (5), [Ni3(tib)2(BTB)2(H2O)2]·14H2O (6), and [Co3(tib)2(BTB)2]·2DMF·6H2O (7) [tib = 1,3,5-tris(1-imidazolyl)benzene, H3BPT = biphenyl-3,4′,5-tricarboxylic acid, H3BTB = 4,4′,4″-benzene-1,3,5-triyl-tribenzoic acid, DMA = N,N-dimethylacetamide, DMF = N,N-dimethylformamide] were achieved and structurally characterized. 1, 2, and 3 are (3,3,4,4)-connected three-dimensional (3D) frameworks with a point symbol of {83}4{85·12}{86}2, while 4, 6, and 7 are also (3,3,4,4)-connected 3D nets but with different framework structures and topologies. 5 is a two-dimensional network, which is further joined together by hydrogen bonds to generate a 3D supramolecular framework. Gas, vapor, and dye adsorption properties of the frameworks were examined, and 1–7 exhibit hysteretic and selective adsorption of CO2 over N2. Furthermore, 7 is a potential adsorbent for removing methylene blue in the aqueous solution.
Co-reporter:Peng Wang;Kai Chen;Qing Liu;Huai-Wei Wang;Mohammad Azam;Saud I. Al-Resayes;Yi Lu
Dalton Transactions 2017 vol. 46(Issue 34) pp:11425-11430
Publication Date(Web):2017/08/29
DOI:10.1039/C7DT02231J
Metal–organic frameworks (MOFs) are gaining considerable attention not only because of their diverse structures but also due to their interesting properties and potential applications. However, fabrication of MOFs with desired structures and properties remains a great challenge. In this study, a strategy based on ligand exchange via single-crystal-to-single-crystal (SCSC) transformation has been undertaken, which can be used to achieve MOFs not available by direct synthesis and also to enrich the family of isoreticular MOFs. Direct X-ray crystallographic observation provides undoubted evidence that the pyrazine (pyz) ligand in [Cu3(L)2(pyz)(H2O)] (L3− = [1,1′:3′,1′′-terphenyl]-4,4′′,5′-tricarboxylate) was replaced by its derivatives without damaging the framework. Furthermore, the catalytic and sorption properties of the MOFs are able to be fine-tuned by introducing definite substituent group decorated on the pore surface. Thus, it is expected that the ligand exchange will be powerful for replacing linker molecules with others having desirable substituents, and as a result to afford desired MOFs.
Co-reporter:Peng Wang;Kai Chen;Qing Liu;Huai-Wei Wang;Mohammad Azam;Saud I. Al-Resayes;Yi Lu
Dalton Transactions 2017 vol. 46(Issue 34) pp:11425-11430
Publication Date(Web):2017/08/29
DOI:10.1039/C7DT02231J
Metal–organic frameworks (MOFs) are gaining considerable attention not only because of their diverse structures but also due to their interesting properties and potential applications. However, fabrication of MOFs with desired structures and properties remains a great challenge. In this study, a strategy based on ligand exchange via single-crystal-to-single-crystal (SCSC) transformation has been undertaken, which can be used to achieve MOFs not available by direct synthesis and also to enrich the family of isoreticular MOFs. Direct X-ray crystallographic observation provides undoubted evidence that the pyrazine (pyz) ligand in [Cu3(L)2(pyz)(H2O)] (L3− = [1,1′:3′,1′′-terphenyl]-4,4′′,5′-tricarboxylate) was replaced by its derivatives without damaging the framework. Furthermore, the catalytic and sorption properties of the MOFs are able to be fine-tuned by introducing definite substituent group decorated on the pore surface. Thus, it is expected that the ligand exchange will be powerful for replacing linker molecules with others having desirable substituents, and as a result to afford desired MOFs.
Co-reporter:Yong-Qing Huang;Yue Zhao;Peng Wang;Taka-aki Okamura;Brian N. Laforteza;Yi Lu;Jin-Quan Yu
Dalton Transactions 2017 vol. 46(Issue 37) pp:12430-12433
Publication Date(Web):2017/09/25
DOI:10.1039/C7DT02883K
A new one-pot synthesis of C2-hydroxypropyl-substituted imidazolinium salts via the ring opening of tetrahydrofuran (THF) with N,N′-disubstituted diamines has been developed. Preliminary studies of the reaction mechanism suggest the CO2-promoted oxidative ring opening of THF followed by Hg(II)-mediated oxidation of an imidazolidine intermediate. These novel C2-substituted imidazolinium salts have shown to be active catalysts for the aza-Diels–Alder reactions.
Co-reporter:Zhi-Qiang Liu;Yue Zhao;Xiu-Du Zhang;Yan-Shang Kang;Qing-Yi Lu;Mohammad Azam;Saud I Al-Resayes
Dalton Transactions 2017 vol. 46(Issue 40) pp:13943-13951
Publication Date(Web):2017/10/17
DOI:10.1039/C7DT02981K
Four new metal–organic frameworks (MOFs) [Zn(L)(bpdc)]·1.6H2O (1), [Co(L)(bpdc)]·H2O (2), [Ni3(L)2(bptc)2(H2O)10]·2H2O (3) and [Cd2(L)(Hbptc)2] (4) were achieved by reactions of the corresponding metal salt with mixed organic ligands of 1,4-di(1H-imidazol-4-yl)benzene (L) and 4,4′-benzophenonedicarboxylic acid (H2bpdc) or biphenyl-2,4′,5-tricarboxylic acid (H3bptc). They exhibit varied structures: MOFs 1 and 4 are porous three-dimensional (3D) frameworks, while 2 is an infinite one-dimensional (1D) chain and 3 is a two-dimensional (2D) network. Remarkably, 1 and 4 can act as potential fluorescent materials for sensing Fe(III) ions and different ketone molecules with high selectivity and sensitivity. In addition, MOF 1 shows selective adsorption of CO2 over N2.
Co-reporter:Zhi-Qiang Liu;Yue Zhao;Peng Wang;Yan-Shang Kang;Mohammad Azam;Saud I. Al-Resayes;Xiao-Hui Liu;Qing-Yi Lu
Dalton Transactions 2017 vol. 46(Issue 28) pp:9022-9029
Publication Date(Web):2017/07/18
DOI:10.1039/C7DT01759F
Herein, two metal–organic frameworks (MOFs), [Co4(μ3-OH)2(L)(BTB)2(H2O)3]·5.6H2O (1) and [Cd3(L)2(BTB)2(μ2-H2O)]·7.4H2O (2), based on 1,3-di(1H-imidazol-4-yl)benzene (L) and 1,3,5-tri(4-carboxyphenyl)benzene (H3BTB), respectively, have been achieved. Compound 1 is a porous three-dimensional (3D) framework with butterfly-like tetranuclear clusters as 7-connected nodes, and compund 2 is a 3D net with a different topology. Remarkably, compounds 1 and 2 exhibit selective adsorption of CO2 over N2 and methyl orange (MO) dye molecules. Magnetic measurements reveal that there are antiferromagnetic interactions within the tetranuclear cluster in 1. Furthermore, 2 was well-dispersed in different solvents, and their luminescent properties were investigated, and the results indicated that 2 could be considered as a potential luminescent probe for the detection of ketone molecules.
Co-reporter:Dan Zhao;Xiao-Hui Liu;Yue Zhao;Peng Wang;Yi Liu;Mohammad Azam;Saud I. Al-Resayes;Yi Lu
Journal of Materials Chemistry A 2017 vol. 5(Issue 30) pp:15797-15807
Publication Date(Web):2017/08/01
DOI:10.1039/C7TA03849F
Excess and deficiency of iron(III) and antibiotics from normal permissible limits will induce serious disorders, so their detection is important but challenging. In this work, by introducing a new amino triazole ligand N1-(4-(1H-1,2,4-triazole-1-yl)benzyl)-N1-(2-aminoethyl)ethane-1,2-diamine (L), a series of Cd(II)-based metal–organic frameworks (MOFs) [Cd3(BDC)3(DMF)2] (1), [Cd(L)(BDC)]2·2DMF·H2O (2), [NaCd2(L)(BDC)2.5]·9H2O (3), [Cd2(L)(2,6-NDC)2]·DMF·5H2O (4) and [Cd2(L)(BPDC)2]·DMF·9H2O (5) were synthesized. MOFs 1, 2 and 3 obtained under the same conditions with the same auxiliary ligand (H2BDC) but different amounts of alkali (NaOH) show distinct 3D, 1D and 3D framework structures, respectively, in which L and BDC2− exhibit varied coordination modes. 4 and 5 with 3D structures were isolated by using longer auxiliary ligands of 2,6-H2NDC and H2BPDC. The porosity and excellent fluorescence performance of 3, 4 and 5 make them potential luminescent sensors for Fe(III) and antibiotics. The results show that 3, 4 and 5 represent high sensitivity for the detection of Fe(III) ions with detection limits of 155 ppb for 3, 209 ppb for 4 and 297 ppb for 5 due to the existence of open channels and chelating NH2 sites. In addition, the strong emissions of 3, 4 and 5 can be quenched efficiently by trace amounts of NFs (nitrofurazone, NZF; nitrofurantoin, NFT; furazolidone, FZD) antibiotics even in the presence of other competing antibiotics such as β-lactams (penicillin, PCL). They are responsive to NZF with detection limits of 162 ppb for 3, 75 ppb for 4 and 60 ppb for 5.
Co-reporter:Ye Deng;Zhao-Yu Yao;Peng Wang;Yue Zhao;Yan-Shang Kang;Mohammad Azam;Saud I. Al-Resayes
RSC Advances (2011-Present) 2017 vol. 7(Issue 71) pp:44639-44646
Publication Date(Web):2017/09/15
DOI:10.1039/C7RA08165K
Under hydro/solvothermal conditions, the assembly of imidazole-containing ligand 1,3,5-tri(1-imidazolyl)benzene (tib) and 2,6-naphthalenedicarboxylic acid (H2NDC) with different transition metal salts provides five new coordination polymers [M2(tib)2(NDC)(H2O)2] SO4·XH2O (1: M = Cd, X = 4; 2: M = Co, X = 4; 3: M = Ni, X = 3), [Cd2(tib)2(NDC)(NO3)2] 2.5DMF·H2O (4) (DMF = N,N-dimethylformamide) and [Zn(tib)2/3(NDC)] (5). 1–3 have the same three-fold interpenetrating 3D framework structures with SO42− as counteranion, while 4 with NO3− as terminal ligand exhibits a wave-like 2D layer structure, which is further extended into a 3D framework by hydrogen bonds. In addition, complex 5 obtained at high temperature is an interesting two-fold interpenetrating 3D structure. Sorption and photoluminescence properties of the complexes were investigated. 4 displays selective adsorption of CO2 over N2. Furthermore, 1 and 4 can be used to probe acetone molecules selectively and rapidly via fluorescence quenching.
Co-reporter:Huai-Wei Wang; Dr. Yi Lu;Bing Zhang;Dr. Jian He;Hua-Jin Xu;Yan-Shang Kang; Dr. Wei-Yin Sun; Dr. Jin-Quan Yu
Angewandte Chemie International Edition 2017 Volume 56(Issue 26) pp:7449-7453
Publication Date(Web):2017/06/19
DOI:10.1002/anie.201703300
AbstractLigand development for rhodium(III)-catalyzed C−H activation reactions has largely been limited to cyclopentadienyl (Cp) based scaffolds. 2-Methylquinoline has now been identified as a feasible ligand that can coordinate to the metal center of Cp*RhCl to accelerate the cleavage of the C−H bond of N-pentafluorophenylbenzamides, providing a new structural lead for ligand design. The compatibility of this reaction with secondary free amines and anilines also overcomes the limitations of palladium(II)-catalyzed C−H amination reactions.
Co-reporter:Yu-Ling Li, Yue Zhao, Peng Wang, Yan-Shang Kang, Qing Liu, Xiu-Du Zhang, and Wei-Yin Sun
Inorganic Chemistry 2016 Volume 55(Issue 22) pp:11821-11830
Publication Date(Web):November 10, 2016
DOI:10.1021/acs.inorgchem.6b01869
Metal–organic frameworks (MOFs) have attracted great attention in the past years due to their diverse structures as well as interesting properties. However, MOFs with multifunctionality are still challenging. Under solvothermal conditions, reactions of 1,3,5-tris(1-imidazolyl)benzene (tib) and 4,4′,4″-benzene-1,3,5-triyl-tribenzoic acid (H3BTB) with Cd(II) salt give rise to two novel MOFs [Cd3(tib)2(BTB)2]·3DEF·4.5H2O (1) and [Cd3(tib)2(BTB)2(DMA)2(H2O)2]·2DMA·8H2O (2) (DEF = N,N-diethylformamide, DMA = N,N-dimethylacetamide) with three-dimensional framework structures. It is fascinating that 1 and 2 not only show unique selectivity for detection of acetone through fluorescence quenching mechanism but also exhibit selective adsorption of gas (CO2 over N2 at 298 K) and dye (methyl orange) molecules.
Co-reporter:Qing Liu, Ji-Min Yang, Li-Na Jin and Wei-Yin Sun
CrystEngComm 2016 vol. 18(Issue 22) pp:4127-4132
Publication Date(Web):22 Jan 2016
DOI:10.1039/C5CE02497H
Porous coordination polymer HKUST-1 [Cu3(BTC)2] (H3BTC = 1,3,5-benzenetricarbocylic acid) nano/microcrystals have been fabricated by an environment friendly facile direct precipitation method at room temperature using inorganic salts such as NaNO3, NaCl, NaBr, KNO3, KCl and KBr as additives. It is found that the concentration of the inorganic salt has an important impact on the morphology and size of the HKUST-1 crystals, and their morphology changed from cube to cuboctahedron and finally to octahedron by increasing the concentration of inorganic salts. Gas adsorption measurements reveal that HKUST-1 nano/microcrystals with different morphologies show high specific surface areas, and their gas sorption properties depend on the crystal morphology and size.
Co-reporter:Pei-Pei Cui, Xiu-Du Zhang, Yue Zhao, Ai-Yun Fu and Wei-Yin Sun
Dalton Transactions 2016 vol. 45(Issue 6) pp:2591-2597
Publication Date(Web):18 Dec 2015
DOI:10.1039/C5DT03091A
Under solvothermal conditions, reactions of pyridine-3,5-bis(phenyl-4-carboxylic acid) (H2L) with lanthanide metal salts give rise to three new metal–organic frameworks (MOFs) with the formula {[Ln4(L)3(μ3-OH)4(H2O)4]·(NO3)2·solvent}n [Ln = Er (1), Yb (2) and Lu (3)]. The complexes were characterized by single crystal and powder X-ray diffraction, IR and thermogravimetric analyses. They have the same two-fold interpenetrating three-dimensional (3D) framework structures with [Ln4(COO)6(μ3-OH)4(H2O)4] clusters as secondary building units (SBUs) and a rare 6-connected lcy topology with the point (Schläfli) symbol of {33·59·63}. Interestingly, 1–3 show selective and hysteretic sorption of CO2 over N2, and the photoluminescence properties of the complexes were also investigated.
Co-reporter:Qing Liu, Ji-Min Yang, Fan Guo, Li-Na Jin and Wei-Yin Sun
Dalton Transactions 2016 vol. 45(Issue 13) pp:5841-5847
Publication Date(Web):23 Feb 2016
DOI:10.1039/C5DT04944J
Nano/microscale lanthanide porous coordination polymer MIL-103(Eu) [Eu(BTB)] (H3BTB = 4,4′,4′′-benzene-1,3,5-triyl-tribenzoic acid) crystals have been fabricated at room temperature by a facile, convenient and environmentally friendly method. The structures of the products were confirmed by powder X-ray diffraction, and the crystal morphologies, including microrods, nanorods and nanospheres, were characterized by scanning electron microscopy. It is found that the addition of sodium acetate and the concentration of the reactants have an important impact on the morphology and size of the MIL-103(Eu) crystals. Gas adsorption measurements reveal that the products show high specific surface areas among the rare earth based coordination polymers and the MIL-103(Eu) nanorods can selectively adsorb CO2 over N2 under ambient conditions. Furthermore, all the products exhibit red emission corresponding to the 5D0 → 7F2 transition of the Eu(III) ion, and MIL-103(Eu) nanorods display sensitive and selective sensing for Cu(II) ions and acetone molecules in solution.
Co-reporter:Zhao-Peng Qi, Ji-Min Yang, Yan-Shang Kang, Fan Guo and Wei-Yin Sun
Dalton Transactions 2016 vol. 45(Issue 21) pp:8753-8759
Publication Date(Web):20 Apr 2016
DOI:10.1039/C6DT00886K
A facile and universal method was developed to evaluate the relative water stability of porous MOFs and morphological evolution was achieved by controlling the volume ratio of DMF and H2O. The relative water stability of the studied MOFs is in the order HKUST-1 > MOF-505 ∼ UMCM-150 > NOTT-101 > DUT-23(Cu) > [Zn2(BPnDC)2(DABCO)] ∼ [Cu3(TPTrC)2(DABCO)] > MOF-5. In addition, DUT-23(Cu) [Cu6(BTB)4(BPY)3] (H3BTB = 4,4′,4′′-benzene-1,3,5-triyl-tribenzoic acid, BPY = 4,4′-bipyridine) nanoparticles obtained with a volume ratio of DMF and H2O of 18:2 show excellent adsorption capacity for methylene blue (MB) (814 mg g−1) with high selectivity compared with methyl orange, rhodamine B, and acid chrome blue K dyes due to the size and the electrostatic repulsion effects in aqueous solution.
Co-reporter:Yu-Ling Li, Dan Zhao, Yue Zhao, Peng Wang, Huai-Wei Wang and Wei-Yin Sun
Dalton Transactions 2016 vol. 45(Issue 21) pp:8816-8823
Publication Date(Web):20 Apr 2016
DOI:10.1039/C6DT00568C
Based on 1,3,5-tris(1-imidazolyl)benzene (tib) and 2,2′-dinitro-4,4′-biphenyldicarboxylic acid (H2dnbpdc), four new metal–organic frameworks [M3(tib)(dnbpdc)3(H2O)2] [M = Mn (1), Cd (2)], [Zn3(tib)2(dnbpdc)2.5(Hdnbpdc)]·4DEF (3), and [Cd(tib)(dnbpdc)(H2O)]·DMF·H2O (4) (DEF = N,N-diethylformamide, DMF = N,N-dimethylformamide) were successfully synthesized. Isomeric 1 and 2 were unusual 8-connected uninodal three-dimensional (3D) frameworks with a point symbol of {33·415·59·6}. Compound 3 was a (3,3,4,4)-connected 4-nodal 3D net with a point symbol of {4·6·8}2{4·62}{4·85}{62·83·10}, whereas 4 was a one-dimensional (1D) chain, which was further linked with neighboring 1D chains by hydrogen bonding interactions to give a 3D framework. It is interesting that 1 displayed ferromagnetic and antiferromagnetic interactions within the trinuclear Mn(II) subunit. We also performed Knoevenagel condensation reactions catalyzed by activated 3 to demonstrate its heterogeneous catalytic property. Furthermore, the adsorption property of 3 was also investigated.
Co-reporter:Pei-Pei Cui, Yue Zhao, Xiu-Du Zhang, Peng Wang, Wei-Yin Sun
Dyes and Pigments 2016 Volume 124() pp:241-248
Publication Date(Web):January 2016
DOI:10.1016/j.dyepig.2015.09.024
•Lanthanide-organic frameworks with tricarboxylate ligands have been obtained.•The frameworks are three-dimensional (3,6)-connected nets with {42.6}2{44.62.87.102} topology.•Luminescence of the frameworks was investigated.Reactions of tricarboxylate ligands biphenyl-3,4′,5-tricarboxylic acid (H3L1) and [1,1′:3′,1″-terphenyl]-4,4″,5′-tricarboxylic acid (H3L2) with the lanthanide metal salts under solvothermal conditions give rise to five new lanthanide-organic frameworks. Complexes {[Ln(L1)(H2O)(DMF)]·DMF·H2O}n [Ln = La (1), Ce (2) and Sm (3)] with (L1)3− have the same framework structures, while the frameworks based on the ligand (L2)3− with formula {[Ln(L2)(H2O)2]·2DMF·14H2O}n [Ln = Sm (4) and Gd (5)] are also isostructural. All the complexes have binuclear paddlewheel [Ln2(CO2)4] clusters as the secondary building units, which are further linked together by the organic ligands to form three-dimensional (3,6)-connected frameworks. In addition, thermal stability and photoluminescence properties of 1–5 were investigated.
Co-reporter:Ye Deng, Yue Zhao, Xiu-Du Zhang, Yan-Shang Kang, Wei-Yin Sun
Microporous and Mesoporous Materials 2016 Volume 231() pp:163-170
Publication Date(Web):1 September 2016
DOI:10.1016/j.micromeso.2016.05.026
•Frameworks with carboxylate and semi-flexible tripodal N-donor ligands have been obtained.•The frameworks show 2D and 3D diverse structures and topologies.•Luminescence and sorption properties of the frameworks were investigated.Five new coordination polymers [Zn3(biimb)2(BPT)2]·4DMF·2.5H2O (1), [Zn(biimb)(NDC)]·1.5H2O (2), [Zn(biimb)(NDC)]·3DMF (3), [Cd(biimb)(NDC)0.5Cl]·3H2O (4) and [Cd3(biimb)2(BPDC)3(H2O)4]·4H2O (5) [biimb = 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene, H3BPT = biphenyl-3,4′,5-tricarboxylic acid, H2NDC = 2,6-naphthalenedicarboxylic acid, H2BPDC = 4,4′-biphenyldicarboxylic acid, DMF = N,N-dimethylformamide] were synthesized by hydro/solvothermal reactions and characterized by elemental, thermogravimetric analyses, IR, powder and single crystal X-ray diffractions. Complex 1 is a (3,3,4,4)-connected 4-nodal 3D framework. The linkage of Zn(II), biimb and NDC2− makes a 2D network structure of 2, in which biimb acts as a bidentate ligand, while in 3, the biimb ligands display as tridentate and connect Zn(II) to compose 2D networks, which are further linked together by NDC2− to generate 3D structure of 3. 4 is a pillared-layer 3D net containing [Cd(biimb)Cl]+ layers and NDC2− pillars. 5 is an interesting 3-fold interpenetrating 3D net. Photoluminescence and gas adsorption properties of the complexes were investigated.
Co-reporter:Ye Deng, Peng Wang, Yue Zhao, Yan-Shang Kang, Wei-Yin Sun
Microporous and Mesoporous Materials 2016 Volume 227() pp:39-47
Publication Date(Web):June 2016
DOI:10.1016/j.micromeso.2016.02.042
•Zn(II) and Cd(II) frameworks with mixed organic ligands have been synthesized.•The frameworks show different 2D and 3D structures.•Gas and dye adsorption properties of the frameworks were investigated.Three new coordination polymers [Zn(tib)(BPDS)] (1), [Zn(tib) (BPDS) (H2O)]·6H2O (2) and [Zn2(tib) (TPDC-4CH3)2]·DMF·10H2O (3) (DMF = N, N-dimethylformamide), and a previously reported one [Cd(tib)2]·2NO3·4DMF (4) were synthesized by hydro/solvothermal reactions of corresponding metal salt with mixed organic ligands of 1, 3, 5-tris(1-imidazolyl)benzene (tib) and 4, 4'-biphenyldisulfonic acid (H2BPDS)/2′, 3′, 5′, 6′-tetramethylterphenyl-4, 4″-dicarboxylic acid (H2TPDC-4CH3). The complexes were characterized by elemental, thermogravimetric analyses, IR, single crystal and powder X-ray diffractions. 1 and 2 are 2D networks with {4·82} and {63} topologies, which are further assembled into 3D architectures through hydrogen bonding interactions. In 3, both tib and TPDC-4CH32− act as bidentate bridging ligands and link Zn(II) centers to form a 3-fold interpenetrating 3D framework, while 4 is a (3, 6)-connected binodal 3D net with the Schläfli symbol of {4·62}2{42·610·83}. Gas and dye sorption and photoluminescence properties of the complexes were investigated.
Co-reporter:Ji-Min Yang, Zhao-Peng Qi, Yan-Shang Kang, Qing Liu, Wei-Yin Sun
Microporous and Mesoporous Materials 2016 Volume 222() pp:27-32
Publication Date(Web):1 March 2016
DOI:10.1016/j.micromeso.2015.09.052
•Template-free synthesis of micro-sized SUMOF-3 was investigated.•The formation mechanism of the resulting crystal morphology was investigated.•The sorption properties are dependent on the morphology and size of particles.SUMOF-3 microcrystals with controllable morphology and size were successfully obtained by solvothermal method and characterized by powder X-ray diffraction (PXRD), field emission scanning electron microscopy (SEM), thermogravimetric analysis (TGA), infrared (IR) and gas adsorption measurements. The influence of additives of polyvinylpyrrolidone (PVP), cetyltrimethylammonium bromide (CTAB), aqueous ammonia (NH3·H2O) and triethylamine (TEA) on morphology and size of SUMOF-3 microcrystals was investigated, and the formation mechanism of the resulting crystal morphology was supposed. The results show that the surfactant of PVP and CTAB as capping agent can affect the coordination interaction between the metal ion and organic linker, while the base of NH3·H2O and TEA as modulator can affect deprotonation of the organic linker, resulting in the formation of SUMOF-3 microcrystals with controllable morphology and size. The results of gas adsorption measurements reveal that the crystalline particles have large surface area and pore volume, implying potential application in the fields of gas adsorption.
Co-reporter:Li Luo, Peng Wang, Qing Liu, Taka-aki Okamura, Gao-Chao Lv, Yi Lu, Wei-Yin Sun
Microporous and Mesoporous Materials 2016 Volume 219() pp:199-208
Publication Date(Web):1 January 2016
DOI:10.1016/j.micromeso.2015.08.009
•Zn(II) and Ni(II) frameworks with mixed organic ligands have been obtained.•The frameworks show different 2D network and 3D structures.•Sorption properties of the frameworks were investigated.Zinc(II) and nickel(II) frameworks [Zn2(L)(BTC)(NO3)]·H2O·2CH3CN (1), [Ni2(L)(H2O)3(HBTC)2]·3.6H2O (2), [Ni(L)(H2O)2](BPDC)·2H2O (3), [Ni(L)(H2O)(BPDC)]·4H2O (4) and [Ni2(L)(MeOH)4(BPDC)2]·2H2O (5) were synthesized by reactions of corresponding metal salts with 3,3′,5,5′-tetra(1H-imidazol-1-yl)-1,1′-biphenyl (L) and multicarboxylic acids of 1,3,5-benzenetricarboxylic acid (H3BTC), 4,4′-biphenyldicarboxylic acid (H2BPDC). Complex 1 is a 2-fold interpenetrating 3D net, while 2 is a 2D network with infinite 1D hinged Ni(II)-L chains linked by HBTC2− ligands. 3, 4 and 5 were obtained by using different molar ratios of L, H2BPDC and Ni(II) salt, and found to show different 2D network structures in which the numbers of coordinated carboxylate groups of BPDC2− are 0, 1 and 2, respectively. Sorption properties of 1–5 were investigated.
Co-reporter:Ji-Min Yang, Zhao-Peng Qi, Yan-Shang Kang, Qing Liu, Wei-Yin Sun
Chinese Chemical Letters 2016 Volume 27(Issue 4) pp:492-496
Publication Date(Web):April 2016
DOI:10.1016/j.cclet.2015.12.031
In(BTC)(phen)(H2O) nanocrystals with controllable morphology and size were successfully obtained by solvothermal method. Hierarchical straw-sheaf-like architectures, nanorods and elongated hexagons have been synthesized by varying the volume ratio of DMF:H2O:C2H5OH. Phase-pure In2O3 nanocrystals were obtained by the calcination of the precursors without significant alteration of the morphology. The products were characterized by PXRD, SEM, TEM, TGA, IR and gas adsorption measurements. The photocatalytic effect was investigated for the In2O3 nanocrystals with different morphology on the degradation of rhodamine B (RhB) and it was found that the nanorods exhibited the best photocatalytic activity, which shows the degradation efficiency of 94% for 8 h. The results showed that the photocatalytic activity increased with the increase of BET surface area and pore volume.Cubic In2O3 was obtained by thermal annealing of the In(BTC)(phen)(H2O) nanocrystals with different size and morphology, and found to show good photocatalytic activity for the degradation of RhB.
Co-reporter:Huai-Wei Wang, Pei-Pei Cui, Yi Lu, Wei-Yin Sun, and Jin-Quan Yu
The Journal of Organic Chemistry 2016 Volume 81(Issue 8) pp:3416-3422
Publication Date(Web):March 18, 2016
DOI:10.1021/acs.joc.6b00083
Rhodium(III)-catalyzed C–H arylation of arenes with phenylboronic acid pinacol esters has been achieved using a readily removable N-pentafluorophenylbenzamide directing group for the first time. The use of a bidentate phosphine ligand (Binap) significantly increased the yield of the cross-coupling of C–H bonds with organoboron reagents.
Co-reporter:Ji-Ai Hua, Yue Zhao, Yan-Shang Kang, Yi Lu and Wei-Yin Sun
Dalton Transactions 2015 vol. 44(Issue 25) pp:11524-11532
Publication Date(Web):13 May 2015
DOI:10.1039/C5DT01386K
Starting from the same metal salts and mixed organic ligands of 1,3,5-tris(1-imidazolyl)benzene (tib) and 2-bromo-1,4-benzenedicarboxylic acid (H2BDC-Br), two novel zinc(II) coordination polymers [Zn2(tib)2(BDC-Br)]2·2SO4·17H2O (1) and [Zn4(tib)2(BDC-Br)3(H2O)4SO4]·7.5H2O·2.5DMF (2) (DMF = N,N-dimethylformamide) were obtained by using different solvent systems of DMF/H2O and DMF/EtOH/H2O, respectively. 1 is an unusual (3,4)-connected 3D net with a Point symbol of {4·8·104}{4·8·10}, while 2 is a complicated 1D chain, which is further connected to form a 3D supramolecular architecture by hydrogen bonding interactions. In particular, 1 and 2 exhibit selective adsorption of CO2 over N2 and show good selectivity for detection of acetone via fluorescence quenching.
Co-reporter:Zhao-Peng Qi, Ji-Min Yang, Yan-Shang Kang and Wei-Yin Sun
Dalton Transactions 2015 vol. 44(Issue 38) pp:16888-16893
Publication Date(Web):24 Aug 2015
DOI:10.1039/C5DT02636A
A facile and controllable synthesis of porous framework [Cu3(L)2(DABCO)] (1) (H3L = 1,1′:3,1′′-terphenyl]-4,4′′,5′-tricarboxylic acid; DABCO = 1,4-diazabicyclo[2.2.2]octane) microcrystals was realized with morphology evolution from a tetragonal plate to an elongated tetragonal bipyramid, and the particle size changes by tuning the volume ratio of mixed solvents of DMF and H2O. Interestingly, the exposed high-energy {103} crystal facet can be easily tuned by controlling the supersaturation through the increase of the solution concentration, resulting in the formation of spindle microcrystals. It was found that both H2O and HCl play important roles in the morphology evolution process. The gas adsorption properties were found to be dependent on the morphology of microcrystals, and the elongated tetragonal bipyramidal microcrystals show the largest BET surface area.
Co-reporter:Yin-Xia Sun and Wei-Yin Sun
CrystEngComm 2015 vol. 17(Issue 22) pp:4045-4063
Publication Date(Web):30 Mar 2015
DOI:10.1039/C5CE00372E
Metal–organic frameworks (MOFs) are assemblies in which metal ions/clusters and organic linkers are combined through coordination interactions. Accordingly, the design and construction of MOFs depends on two primary interacting components, namely the connectors (metal ions/clusters) and linkers (organic ligands). The judicious selection of organic ligands to coordinate with suitable metal centers is a key factor in determining the structures and properties of MOFs. The donor atom type, coordination mode, rigidity/flexibility, functional and/or substituent groups and the geometry of the organic ligands have a remarkable influence on the structures of MOFs. In this review, we highlight zinc(II) and cadmium(II) MOFs with 1-imidazole-containing and 1-imidazole-carboxylate ligands. The influence of the nature of the organic ligands on the assembly and structural modulation of the MOFs is discussed, so as to provide primary information and insights into the design and assembly of the desired Zn(II) and Cd(II) MOFs.
Co-reporter:Ji-Min Yang, Qing Liu, Yan-Shang Kang and Wei-Yin Sun
CrystEngComm 2015 vol. 17(Issue 26) pp:4825-4831
Publication Date(Web):18 May 2015
DOI:10.1039/C5CE00706B
Well-dispersed hierarchical flower-like and net-like architectures of UMCM-150 were successfully prepared by a facile and rapid method at room temperature. Owing to the high surface area and pore volume, the UMCM-150 flower-like nanostructures exhibit excellent adsorption capability for the dye of methylene blue (MB) with a maximum capacity of 560 mg g−1, which is higher than that of most materials reported to date. The influence of variables such as initial pH and MB concentration, contact time and shape of UMCM-150 nanostructures was investigated. The results indicate that the UMCM-150 nanostructures have promising application in the MB dye containing wastewater treatment.
Co-reporter:Ji-Ai Hua, Yue Zhao, Dan Zhao, Yan-Shang Kang, Kai Chen and Wei-Yin Sun
RSC Advances 2015 vol. 5(Issue 54) pp:43268-43278
Publication Date(Web):07 May 2015
DOI:10.1039/C5RA06072A
Four new Cd(II) frameworks [Cd(tib)(p-BDC-OH)]·H2O (1), [Cd(tib)(m-BDC-OH)]·3H2O (2), [Cd(tib)(m-BDC-CH3)]·3H2O (3) and [Cd(tib)(m-BDC-CH3)]·11H2O (4) (tib = 1,3,5-tris(1-imidazolyl)benzene, p-H2BDC-R = 2-R-1,4-benzenedicarboxylic acid, m-H2BDC-R = 5-R-1,3-benzenedicarboxylic acid, R = OH or CH3) have been successfully synthesized under solvothermal conditions. 1 is a 3D framework with a Point symbol of {810}{83} constructed from Cd-tib 3D net and Cd-p-BDC-OH 1D helical chain. 2 and 3 possess different 3D structures with the same topology of {4·62}{4·66·83} built from Cd-tib 2D networks and Cd-m-BDC-R 1D linear chains, while 4 is a 2D network with {42·67·8}{42·6} topology based on Cd-tib and Cd-m-BDC-CH3 1D chains. The results show that the dicarboxylate ligands and reaction medium play important role in determining the structures of MOFs. Moreover, ferroelectric and photoluminescence properties of the complexes were studied.
Co-reporter:Yu-Ling Li, Ji-Ai Hua, Yue Zhao, Yan-Shang Kang, Wei-Yin Sun
Microporous and Mesoporous Materials 2015 Volume 214() pp:188-194
Publication Date(Web):15 September 2015
DOI:10.1016/j.micromeso.2015.04.035
•Metal-organic frameworks with mixed organic ligands have been obtained.•The frameworks show 1D chain, non- and three-fold interpenetrated 3D structures.•Anion exchange and sorption properties of the frameworks were investigated.Six new metal-organic frameworks [M2(tib)2(bpdc)(H2O)2]·SO4·2H2O [M = Ni (1), Co (2), Cu (3)], [Co(tib)(dnbpdc)(H2O)]·DMF·H2O (4), [M2(tib)2(bpndc)(H2O)5]·(bpndc)·5H2O [M = Ni (5), Mn (6)], [tib = 1,3,5-tris(1-imidazolyl)benzene, H2bpdc = 4,4′-biphenyldicarboxylic acid, H2dnbpdc = 2,2′-dinitro-4,4′-biphenyldicarboxylic acid, H2bpndc = 4,4′-benzophenonedicaboxylic acid, DMF = N,N-dimethylformamide] have been synthesized and characterized by single-crystal and powder X-ray diffractions, infrared spectra (IR), elemental and thermogravimetric analyses. Complexes 1, 2 and 3 are (3, 4)-connected 2-nodal three-dimensional (3D) frameworks with point (Schläfli) symbol of {4·6·8}{4·62·8·102}, while 4 is one-dimensional (1D) chain, which is further linked together by hydrogen bonding interactions to give a 3D framework. Complexes 5 and 6 are 3D frameworks with the point (Schläfli) symbol of {4·142}. Anion exchange and adsorption properties of 1 were studied.
Co-reporter:Pei-Pei Cui, Xiu-Du Zhang, Yue Zhao, Kai Chen, Peng Wang, Wei-Yin Sun
Microporous and Mesoporous Materials 2015 Volume 208() pp:188-195
Publication Date(Web):15 May 2015
DOI:10.1016/j.micromeso.2015.02.005
•Metal complexes with pyridine-3,5-bis(phenyl-4-carboxylate) have been obtained.•The complexes show different framework structure and topology.•Photoluminescence and sorption property of the complexes were investigated.Four new metal-organic frameworks {[Zn(L)]·2.6H2O}n (1), [Cd(L)(H2O)(DMA)]n (2), [Co3(L)2(HCOO)2(H2O)2]n (3) and {[Mn(L)(H2O)]·DMF}n (4) [H2L = pyridine-3, 5-bis(phenyl-4-carboxylic acid), DMA = N,N-dimethylacetamide, DMF = N,N-dimethylformamide] have been synthesized and characterized by single crystal and powder X-ray diffractions, IR and thermogravimetric analyses. 1 is a three-dimensional (3D) framework with {46·64} topology, while 2 is a 3D framework formed by parallel/parallel inclined interpenetration of two-dimensional (2D) networks with {63} topology. 3 processes a 3D framework structure with point symbol of {4·82}2{42·812·10}, and 4 shows bilayer structure with {43·63} topology, which is further assembled into a 3D supramolecular architecture by hydrogen bonding interactions. Gas adsorption property of 1, 2 and 4, photoluminescence of 1 and 2 as well as magnetic property of 4 were investigated.
Co-reporter:Kai Chen ; Yan-Shang Kang ; Yue Zhao ; Ji-Min Yang ; Yi Lu
Journal of the American Chemical Society 2014 Volume 136(Issue 48) pp:16744-16747
Publication Date(Web):November 14, 2014
DOI:10.1021/ja5098836
Multidimensional supramolecular assemblies based on cucurbit[n]uril (n = 6 or 7) were constructed via the outer-surface interactions of cucurbit[n]urils with the polyaromatic compound 4,4′,4″-benzene-1,3,5-triyl-tribenzoate as a structure-directing agent. Most impressively, the cucurbit[6]uril-based assembly exhibits high selectivity for capture of cesium cations among the common alkali metal ions in a basic medium and releases the cesium cations under acidic conditions. This reversible process enables possible applications in cesium cation capture.
Co-reporter:Xiao-Liang Zhao and Wei-Yin Sun
CrystEngComm 2014 vol. 16(Issue 16) pp:3247-3258
Publication Date(Web):23 Jan 2014
DOI:10.1039/C3CE41791C
Metal–organic frameworks (MOFs) are coordination compounds with infinite structures consisting of metal ions/clusters and organic ligands linked through coordination interactions. The reported studies prove the fact that the nature of the organic ligands dominates the final structures as well as properties of functional MOFs in a certain way. Therefore, we focus on discussing the ligands to fabricate functional MOFs which are suitable for catalysis and the storage of hydrogen and carbon dioxide. With the development of functional MOFs, diverse N- or O-donor ligands have been designed. However, sometimes just one ligand containing only one kind of N- or O-donor cannot realize the specific functionality of frameworks. Thus it is necessary to design a ligand containing N- and O-donors simultaneously or mixed ligands with the same or different donors. In this highlight we summarize some common types of mixed donors or mixed organic ligands used in the construction of functional MOFs and discuss the relationship between the organic ligands and the final structures.
Co-reporter:Li-Na Jin, Qing Liu and Wei-Yin Sun
CrystEngComm 2014 vol. 16(Issue 19) pp:3816-3828
Publication Date(Web):12 Feb 2014
DOI:10.1039/C3CE41962B
In recent years, nanoscale metal–organic coordination polymers have attracted more and more attention because of their specific properties in gas sorption, sensors, contrast agents, drug delivery, templates and so on. Carboxylate compounds are a large family of O-donor ligands and are studied widely because such ligands can be designed with various structures and can also form strong bonds with metal centers. Until now, many nanoscale metal–organic coordination polymers with carboxylate-containing ligands have been reported. The purpose of this tutorial highlight is to present recent advances in the syntheses of nanoscale metal–carboxylate coordination polymers and illustrate the potential application of this new class of nanomaterials in different areas.
Co-reporter:Pei-Pei Cui, Yue Zhao, Gao-Chao Lv, Qing Liu, Xiao-Liang Zhao, Yi Lu and Wei-Yin Sun
CrystEngComm 2014 vol. 16(Issue 28) pp:6300-6308
Publication Date(Web):06 Jan 2014
DOI:10.1039/C3CE42260G
Three new metal–organic frameworks (MOFs) {[Zn(L)(HCOO)(H2O)]·H2O}n (1), {Cd(L)2}n (2) and {Co(L)(BDC)0.5(H2O)}n (3) [HL = 3,5-di(pyridine-4-yl)benzoic acid, H2BDC = 1,4-benzenedicarboxylic acid] were synthesized by hydro/solvothermal reactions and characterized by elemental analysis, thermogravimetric analysis, IR spectroscopy, powder and single crystal X-ray diffraction. Complex 1 is a two-dimensional (2D) network with {63} topology, which is further assembled into a three-dimensional (3D) supramolecular architecture through hydrogen bonding interactions. Complex 2 is a 2-fold interpenetrating 3D framework with a point (Schläfli) symbol of {63}{67·83}, while 3 is a 3D net formed by interpenetration of 2D bilayers (2D + 2D → 3D) with a point (Schläfli) symbol of {63}{66}. Selective and hysteretic sorption of carbon dioxide (CO2) was found for 3 at 195 K, and the photoluminescence properties of 1 and 2 were investigated.
Co-reporter:Ji-Ai Hua, Yue Zhao, Qing Liu, Dan Zhao, Kai Chen and Wei-Yin Sun
CrystEngComm 2014 vol. 16(Issue 32) pp:7536-7546
Publication Date(Web):29 May 2014
DOI:10.1039/C4CE00835A
By introducing 1,4-benzenedicarboxylic acid (H2BDC) with different substituent groups H2BDC-R (R = NH2, OH, NO2) into the Zn(II)-1,3,5-tris(1-imidazolyl)benzene (tib) system, four new zinc(II) coordination polymers, namely [Zn5(tib)2(BDC-NH2)4(μ2-OH)2]·H2O (1), [Zn2(tib)(BDC-NH2)SO4(H2O)2]·5H2O (2), [Zn2(tib)2(HBDC-OH)2(BDC-OH)]·2H2O (3) and [Zn(tib)(BDC-NO2)]·H2O (4), have been successfully synthesized under solvothermal conditions. Complexes 1 and 2 based on the same H2BDC-NH2 show different structures: 1 is a 3-fold interpenetrated 3D framework with point (Schläfli) symbol {53·62·7}2{53}2{58·62·85}, while 2 exhibits a 2D network with {62·84}{62·8}4 topology. 3 and 4 are 2D networks with different topologies of {63} and {44·62}, respectively. The structural diversity of 1–4 indicates that the substituent groups of H2BDC as well as the reaction temperature and solvent play an important role in determining the framework structures and topologies. Furthermore, the sorption and photoluminescence properties of the complexes were investigated.
Co-reporter:Yue Zhao, Kai Chen, Jian Fan, Taka-aki Okamura, Yi Lu, Li Luo and Wei-Yin Sun
Dalton Transactions 2014 vol. 43(Issue 5) pp:2252-2258
Publication Date(Web):25 Oct 2013
DOI:10.1039/C3DT52655K
A family of silver(I) complexes, [Ag2(L)2(OOCCF3)2] (1), [Ag(L)0.5(OOCCF3)] (2), [Ag(L)2](OOCCF3)(H2O)2 (3), was obtained by reactions of 4,4′-di(2-oxazolinyl)biphenyl (L) and AgOOCCF3 in different reaction media. Compound 1 has a 1D chain structure with alternative connections between the Ag(I) and L ligand. When the crystal nucleation inductor, pyrazine, was added into the reaction system, complex 2 was isolated with no pyrazine observed in its structure. In 2, the 1D inorganic chains formed by Ag(I) cations and OOCCF3− anions were connected by the L ligand to produce a 2D network. When a different inductor, imidazole, was added into the reaction system, 3 with (4,4) topology was synthesized, and again no imidazole was found in 3. When 1–3 were used as catalysts for cycloaddition reactions between imino esters and methyl acrylate, 3 affords the highest yield, in which the particular size of the channels in 3 led to its selective catalytic performance.
Co-reporter:Shui-Sheng Chen, Peng Wang, Satoshi Takamizawa, Taka-aki Okamura, Min Chen and Wei-Yin Sun
Dalton Transactions 2014 vol. 43(Issue 16) pp:6012-6020
Publication Date(Web):09 Jan 2014
DOI:10.1039/C3DT53388C
The use of a 4-imidazole containing tripodal ligand 1,3,5-tri(1H-imidazol-4-yl)benzene (H3L) enabled isolation of two three-dimensional (3D) porous metal–organic frameworks (MOFs) [Zn(HL)]·solvent (1) and [Cd(H3L)2](ClO4)2·10.5H2O (2) featuring 4,4- and 3,6-connected nets related to the structures of ecl and pyrite, respectively. Framework 1 has 3D channels based on Zn–Im− (Im− = imidazolate) moieties due to partial deprotonation of the 1H-imidazol-4-yl groups of H3L while porous framework 2 is constructed by the coordination of neutral H3L ligands with Cd(II). Desolvated solid 1′ showed remarkable uptake for CO2, N2, H2, CH4 gases as well as the volatile organic vapor of MeOH, EtOH, i-PrOH and C6H6, significantly, exhibiting temperature dependent selective gas sorption for CO2 over N2. Grand Canonical Monte Carlo (GCMC) simulations were performed to elucidate the mechanism of the selective gas adsorption. Cage-like motifs are found in pyrite-net 2, in which ClO4− anions are hosted, and the results of IR, elemental analysis and PXRD measurements confirm that 2 has a reversible anion exchange property among perchlorate, nitrate and nitrite anions.
Co-reporter:Ji-Min Yang, Qing Liu, Yan-Shang Kang and Wei-Yin Sun
Dalton Transactions 2014 vol. 43(Issue 44) pp:16707-16712
Publication Date(Web):23 Sep 2014
DOI:10.1039/C4DT02429J
IRMOF-3 nano/microcrystals with controllable morphologies and sizes were successfully obtained by a simple solvothermal method. The shape evolution of IRMOF-3 crystals from cube to truncated cube, cuboctahedron, truncated octahedron and finally to octahedron was achieved by adjusting the amount of surfactant. The surfaces of the IRMOF-3 nano/microstructures are affected by the reaction temperature, and the nano/microparticles show shape-dependent sorption properties.
Co-reporter:Li-Na Jin, Qing Liu, Ying Yang, Hong-Gang Fu, Wei-Yin Sun
Journal of Colloid and Interface Science 2014 Volume 426() pp:1-8
Publication Date(Web):15 July 2014
DOI:10.1016/j.jcis.2014.03.066
•Indium-based coordination polymer particles (In-CPPs) were prepared by solvothermal method.•The In-CPPs have hierarchical nanostructures and exhibit high surface area and pore volume.•The In-CPPs exhibit excellent adsorption capability for Congo red in water treatment.•Morphology-preserved porous In2O3 were derived from In-CPPs.The removal of dyes in wastewater has been of much interest in the recent decades because dyes are stable, toxic and even potentially carcinogenic, and their release into environment causes serious environmental, aesthetical, and health problems. In the current work, indium-based coordination polymer particles (In-CPPs) have been fabricated via a facile solvothermal synthesis without any template or surfactant. In-CPPs are composed of hierarchical nanostructures assembled from abundant nanoplates with thickness of about 20 nm. Owing to their high BET surface area and pore volume, In-CPPs exhibit excellent adsorption capability for Congo red with a maximum capacity of 577 mg g−1, which was higher than that of most materials reported to now. In-CPPS can also be outstanding adsorbents for removing other dyes such as acid chrome blue K, brilliant red GR and brilliant green. Furthermore, after calcinations in air In-CPPs can be converted to morphology-preserved porous In2O3 products which can detect NOx gas in air at room temperature.
Co-reporter:Ling-Ling Zhai, Yue Zhao, Li Luo, Peng Wang, Qing Liu, Kai Chen, Wei-Yin Sun
Microporous and Mesoporous Materials 2014 Volume 187() pp:86-93
Publication Date(Web):15 March 2014
DOI:10.1016/j.micromeso.2013.12.019
•Nickel(II) frameworks with mixed ligands have been obtained.•Adsorption property of the complexes were investigated.•Complexes catalyze acetalization reaction of aldehydes with methanol.Four new Ni(II) complexes [Ni(L)(SO4)(H2O)2]·H2O (1), [Ni3(L)4(p-BDC)3(H2O)6]·6H2O (2), [Ni(L)(m-BDC)(H2O)2]·0.5H2O (3) and [Ni(L)(BPDC)(H2O)2] (4) have been prepared by reactions of 3,5-di(1H-benzimidazol-1-yl)pyridine (L) with nickel sulfate in the presence of auxiliary ligands of phthalic acid (o-H2BDC), terephthalic acid (p-H2BDC), isophthalic acid (m-H2BDC) and biphenyl-4,4′-dicarboxylic acid (H2BPDC), respectively. Interestingly, phthalate (o-BDC2−) did not take part in formation of 1, instead SO42- was found in 1. Complex 2 with p-BDC2− shows different two-dimensional (2D) network from 1 while 3 has one-dimensional (1D) chain structure. Complex 4 is a three-dimensional (3D) framework with CdSO4 topology. The thermal stability and adsorption property of the complexes were investigated. Furthermore, it was found that complexes 1–4 can catalyze acetalization reaction of aldehydes with methanol, and 1 gives the highest yield.
Co-reporter:Ji-Min Yang, Wei Zhang, Qing Liu and Wei-Yin Sun
RSC Advances 2014 vol. 4(Issue 93) pp:51098-51104
Publication Date(Web):24 Sep 2014
DOI:10.1039/C4RA08736D
Porous ZnO and ZnO–NiO composite nano/microspheres have been successfully synthesized by the calcination of non-doped and Ni(II)-doped precursors in air, respectively. The catalytic effect was investigated for porous ZnO and ZnO–NiO composite nano/microspheres for the thermal decomposition of ammonium perchlorate (AP). The ZnO–NiO composite nano/microspheres showed remarkable catalytic effect for the thermal decomposition of AP. The decomposition temperature was decreased by 144.5 °C, and the apparent activation energy was significantly decreased to 117.8 kJ mol−1, which is considerably lower than 159.7 kJ mol−1 for pure AP. The catalytic capacity of ZnO–NiO composite nanostructures is higher than that of most of the materials reported to date. As a result, porous ZnO–NiO composite nano/microstructures could be a promising candidate material for an AP-based propellant. In addition, using the as-prepared porous ZnO microspheres, we have successfully prepared a novel, ultrahigh resolution electrochemical impedance DNA biosensor for the enhanced detection of the PML/RARA fusion gene in acute promyelocytic leukemia with a detection limit of 2.2 × 10−13 mol L−1; therefore, it can act as a biosensing materials for the recognition of DNA hybridization.
Co-reporter:Chao Hou, Yue Zhao, Wei-Yin Sun
Inorganic Chemistry Communications 2014 Volume 39() pp:126-130
Publication Date(Web):January 2014
DOI:10.1016/j.inoche.2013.11.009
•Two new metal–organic frameworks with mixed ligands have been obtained.•The complexes have new network topologies.•The magnetic properties have been investigated.Two new metal complexes with mixed nitrogen-donor heterocyclic monocarboxylate and dicarboxylate ligands {[Co2(L)2(BDC)(H2O)]·2H2O·6DMF}n (1) and [Mn(L)(OX)0.5]n (2) (HL = 3,5-di(pyridine-4-yl)benzoic acid, H2BDC = 1,4-benzenedicarboxylic acid, H2OX = oxalic acid) have been prepared and characterized by single crystal and powder X-ray diffractions, IR, and thermogravimetric analyses. Crystallographic and topological analyses identify that both complexes have new framework topologies. Complex 1 is a (3,8)-connected 2-nodal 3D net with a point (Schläfli) symbol of (42.5)2(44.510.67.76.8), while 2 is a (4,5)-connected binodal net with a point (Schläfli) symbol of (42.63.8)(42.65.83). Furthermore, magnetic investigation shows that both complexes exhibit overall weak antiferromagnetic coupling between the adjacent metal centers.New Co(II) and Mn(II) coordination frameworks {[Co2(L)2(BDC)(H2O)]·2H2O·6DMF}n (1) and [Mn(L)(OX)0.5]n (2) have been prepared by reactions of ligands of 3,5-di(pyridine-4-yl)benzoic acid (HL), 1,4-benzenedicarboxylic acid (H2BDC) and oxalic acid (H2OX) with corresponding metal salt and characterized.
Co-reporter:Yin-Xia Sun, Wei-Yin Sun
Chinese Chemical Letters 2014 Volume 25(Issue 6) pp:823-828
Publication Date(Web):June 2014
DOI:10.1016/j.cclet.2014.04.032
Reaction temperature is one of the key parameters in the synthesis of metal-organic frameworks (MOFs). Though there is no convergence with regard to the various experimental parameters, reaction temperature has been found to have remarkable influence on the formation and structure of MOFs, especially toward the control of topology and dimensionality of the MOF structures. Theoretically, the reaction temperature affects directly the reaction energy barrier in reaction thermodynamics and the reaction rate in the reaction kinetics. This review aims to show the influence of reaction temperature on crystal growth/assembly, structural modulation and transformation of MOFs, and to provide primary information and insights into the design and assembly of desired MOFs.This review illustrates the influence of temperature on crystal growth/assembly, structural modulation and transformation of MOFs, and provides primary information and insights into the design and assembly of desired MOFs.Figure optionsDownload full-size imageDownload as PowerPoint slide
Co-reporter:Zhi-Hao Chen, Yue Zhao, Peng Wang, Shui-Sheng Chen, Wei-Yin Sun
Polyhedron 2014 Volume 67() pp:253-263
Publication Date(Web):8 January 2014
DOI:10.1016/j.poly.2013.09.010
Eight new coordination polymers [Zn(L)(cis-1,2-CHDA)] (1), [Zn(L)(trans-1,3-CHDA)]·2.5H2O (2), [Zn(L)(cis-1,3-CHDA)]·H2O (3), [Cd(L)(cis-1,2-CHDA)]·3H2O (4), [Cd2(L)2(cis-1,2-CHDA)2]·3H2O (5), [Cd(L)(cis-1,3-CHDA)]·H2O (6), [Cd(L)(cis-1, 4-CHDA)]·5H2O (7) and [Cd(L)(cis-1,4-CHDA)] (8) were synthesized by reactions of corresponding metal salt with 1,3-di(1H-imidazol-4-yl)benzene (L) and different carboxylic acids such as 1,2-cyclohexanedicarboxylic acid (1,2-H2CHDA), 1,3-cyclohexanedicarboxylic acid (1,3-H2CHDA) and 1,4-cyclohexanedicarboxylic acid (1,4-H2CHDA), respectively. The results of crystal structure analysis revealed that 4, 7 and 8 are chains, 1, 3, 5 and 6 are (3)-connected 2D networks with Point (Schläfli) symbol of (63), while 2 is a (3,3)-connected 2D network with Point (Schläfli) symbol of (44,62). Thermal stability and photoluminescence of the complexes were investigated. Furthermore, DFT calculations were carried out on 2–5, and 7 and 8 to discuss the temperature dependent reaction of the complexes.Eight new coordination polymers with different cyclohexanedicarboxylate and rigid ditopic 4-imidazole-containing ligands have been obtained and found to show different structures. The results revealed that the reaction temperature has effect on the manifestation of the resulting structures.
Co-reporter:Ji-Min Yang, Qing Liu, Wei-Yin Sun
Microporous and Mesoporous Materials 2014 190() pp: 26-31
Publication Date(Web):
DOI:10.1016/j.micromeso.2014.01.020
Co-reporter:Kai Chen, Yan-Shang Kang, Li Luo, Yue Zhao, Peng Wang, Qing Liu, Yi Lu, Wei-Yin Sun
Polyhedron 2014 79() pp: 239-249
Publication Date(Web):
DOI:10.1016/j.poly.2014.05.020
Co-reporter:Hai-Wei Kuai, Taka-aki Okamura, Wei-Yin Sun
Polyhedron 2014 72() pp: 8-18
Publication Date(Web):
DOI:10.1016/j.poly.2014.01.019
Co-reporter:Qing Liu;Ji-Min Yang;Dr. Li-Na Jin ;Dr. Wei-Yin Sun
Chemistry - A European Journal 2014 Volume 20( Issue 45) pp:14783-14789
Publication Date(Web):
DOI:10.1002/chem.201402923
Abstract
Herein, we report a facile and convenient method for the synthesis of the porous coordination polymer MOF-14 [Cu3(BTB)2] (H3BTB=4,4′,4′′-benzene-1,3,5-triyl-tribenzoic acid) as microcrystals with definite shapes and crystal facets controlled by the reaction medium at room temperature. The amount of sodium acetate added to the reaction system plays a crucial role in the shape evolution of MOF-14 from rhombic dodecahedrons to truncated rhombic dodecahedrons and cubes with truncated edges and then to cubes. The addition of a base could accelerate the formation rate of crystal growth and increase the supersaturation of crystal growth, thus resulting in the formation of MOF-14 cube crystals with high-energy crystal facets. The morphological evolution was also observed for HKUST-1 [Cu3(BTC)2] (H3BTC=1,3,5-benzenetricarbocylic acid) from octahedrons to cubes, thus verifying the probable mechanism of the morphological transformation. The gas-adsorption properties of MOF-14 with different shapes were studied and reveal that the porous coordination-polymer microcrystals display excellent and morphology-dependent sorption properties.
Co-reporter:Li Luo, Kai Chen, Qing Liu, Yi Lu, Taka-aki Okamura, Gao-Chao Lv, Yue Zhao, and Wei-Yin Sun
Crystal Growth & Design 2013 Volume 13(Issue 6) pp:2312-2321
Publication Date(Web):April 26, 2013
DOI:10.1021/cg301815w
Five new metal complexes, [Zn3(L1)2(BTC)2]·6H2O (1), [Zn3(L1)(BTC)2] (2), [Cd3(L1)(BTC)2] (3), [Cd3(L2)(BTC)2]·4H2O (4), and [Cd3(L2)(BTC)2(H2O)2] (5), have been successfully synthesized by solvothermal reactions of corresponding metal salts with 1,3,5-benzenetricarboxylic acid (H3BTC) and imidazole-containing ligands 1,3,5-tris(imidazol-1-ylmethyl)benzene (L1) and 3,3′,5,5′-tetra(imidazol-1-yl)-1,1′-biphenyl (L2). The structures of the complexes were determined by single crystal X-ray diffraction analysis. Complexes 1 and 2 obtained at different reaction temperatures show different structures: 1 is a three-dimensional (3D) net with Zn-BTC3– layers pillared by L1 ligands, while 2 has a 3D structure with a Zn-BTC3– framework and Zn-L1 chain. Complexes 2 and 3, which contain different metal centers, have similar framework structures but different coordination modes of carboxylate groups. 4 and 5 that were prepared from different solvents show different 3D structures. The thermal stability, photoluminescence, and sorption properties of the complexes were investigated.
Co-reporter:Li-Na Jin, Qing Liu and Wei-Yin Sun
CrystEngComm 2013 vol. 15(Issue 23) pp:4779-4784
Publication Date(Web):10 Apr 2013
DOI:10.1039/C3CE40113H
Size-controlled In2O3 hollow structures have been successfully prepared by a two-step process. Indium(III)–benzenedicarboxylate (In–BDC) hexagonal rods with different sizes were first obtained on a large scale via a simple solution reaction using indium(III) nitrate and 1,4-benzenedicarboxylic acid as starting reactants and DMF as solvent with addition of sodium acetate. Then In2O3 hollow structures were prepared by annealing In–BDC complexes. It was found that the concentration of sodium acetate is important in determining the size of In–BDC hexagonal rods as well as the formation of In2O3 hollow structures. The products were characterized by X-ray diffraction (XRD), energy dispersive spectrometry (EDS), selected area electron diffraction (SAED), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high-resolution TEM (HRTEM). In addition, In2O3 hollow structures were further studied by Raman and room-temperature photoluminescence.
Co-reporter:Qing Liu, Li-Na Jin and Wei-Yin Sun
CrystEngComm 2013 vol. 15(Issue 41) pp:8250-8254
Publication Date(Web):21 Aug 2013
DOI:10.1039/C3CE41133H
Size-controlled metal–imidazolate framework crystals have been synthesized by combining the coordination modulation method and ultrasonic-assisted synthesis for the first time. Aqueous ammonia was used as the coordination modulator, and was found to be able to control the crystal size. The as-obtained crystals had improved adsorption properties compared with that of the bulk ones.
Co-reporter:Li Luo, Gao-Chao Lv, Peng Wang, Qing Liu, Kai Chen and Wei-Yin Sun
CrystEngComm 2013 vol. 15(Issue 45) pp:9537-9543
Publication Date(Web):31 Jul 2013
DOI:10.1039/C3CE41056K
An exploration of reactions of 3,3′,5,5′-tetra(1H-imidazol-1-yl)-1,1′-biphenyl (L) and 1,3,5-benzenetricarboxylic acid (H3BTC) with Co(II) salt has led to the formation of three new complexes with different framework structures, [Co2(L)(HBTC)2(μ2-H2O)(H2O)2]·3H2O (1), [Co3(L)2(BTC)2]·4H2O (2) and [Co2(L)(BTC)(μ2-OH)(H2O)2]·2H2O (3). They were obtained as pH-dependent products. The H3BTC ligand is partially deprotonated in 1, but completely in 2 and 3. Furthermore, a bridging OH− is present in 3. Complex 1 consists of infinite Co(II)–L chains bridged into a layered structure via carboxylate groups of HBTC2−. In case of 2, it has a Co(II)–L 2D network which is further linked by BTC3− resulting the formation of a final 2D structure (2D + 2D → 2D). While in 3, it is a 3D framework with Co(II)–L layers connected by BTC3−. The results showed that the pH plays an important role in determining the structure of the frameworks. The sorption properties of the complexes were investigated.
Co-reporter:Xin Zhou, Yi Lu, Ling-Ling Zhai, Yue Zhao, Qing Liu and Wei-Yin Sun
RSC Advances 2013 vol. 3(Issue 6) pp:1732-1734
Publication Date(Web):06 Dec 2012
DOI:10.1039/C2RA22390B
An economic, efficient and green silver oxide nanoparticle catalyzed three-component coupling reaction of aldehydes, amines and alkynes was developed. This method provided various propargylamines in moderate to high yield at room temperature in air. The silver oxide nanoparticles could be separated simply and reused without significant decrease of activity.
Co-reporter:Chao Hou, Qing Liu, Peng Wang, Wei-Yin Sun
Microporous and Mesoporous Materials 2013 Volume 172() pp:61-66
Publication Date(Web):15 May 2013
DOI:10.1016/j.micromeso.2013.01.020
Two new metal–organic frameworks {[Ni(L)2] ·4H2O}n (1) and {[Co(L)2]·4H2O}n (2) have been prepared by reactions of 3,5-di(pyridine-4-yl)benzoic acid (HL) with corresponding metal salt under solvothermal conditions, and characterized by single crystal and powder X-ray diffractions, IR, elemental and thermogravimetric analyses. 1 and 2 have the same 2-fold interpenetrating three-dimensional structure with ins topology and are porous frameworks upon desolvation. More importantly, the desolvated samples of 1 and 2 show high thermal stability, vapor adsorption of H2O, MeOH or EtOH, and high enthalpy for CO2 adsorption and high selectivity for CO2 over N2 at 298 K, implying the potential application of the coordination polymers for capture and separation of CO2.Graphical abstractHighlights► Porous metal–organic frameworks with ins topology. ► High thermal stability and high enthalpy for CO2 adsorption. ► Selective sorption behavior of CO2 over N2 at 298 K.
Co-reporter:Peng Wang, Li Luo, Jian Fan, Gao-Chao Lv, You Song, Wei-Yin Sun
Microporous and Mesoporous Materials 2013 Volume 175() pp:116-124
Publication Date(Web):15 July 2013
DOI:10.1016/j.micromeso.2013.03.021
Highlights•Copper(II) frameworks with 5-[2-(pyridin-4-yl)vinyl]isophthalate.•Selective sorption behavior of CO2 over N2.•Magnetic property and DFT calculation.A series of copper(II) complexes have been synthesized by reactions of ligand 5-[2-(pyridin-4-yl)vinyl]isophthalic acid (H2L) with Cu(NO3)2·3H2O via the alternation of reaction temperature and solvent system. The complexes were characterized by IR, single crystal and powder X-ray diffractions, and thermogravimetric analysis. {[Cu(HL)2]·2H2O}n (1) has a 1D hinged chain structure, while [CuL]n (2) is a (3,6)-connected 2D network with kgd topology. {[CuL]·0.5H2O}n (3) and [Cu2(L)2(H2O)]n (4) are (3,6)-connected 3D ScD0.33 net and flu-3,6-C2/c net, respectively. Interestingly, the E-form of free ligand is converted into Z-form during the formation of the complexes. The dehydrated complex 3 exhibits different sorption behavior for N2 and CO2. The magnetic properties of 1–4 were also investigated, and both experimental results and DFT calculations indicate that the more carboxylate groups bridging metal ions the stronger magnetic coupling observed in this system.Graphical abstract
Co-reporter:Li-Na Jin, Qing Liu, Wei-Yin Sun
Chinese Chemical Letters 2013 Volume 24(Issue 8) pp:663-667
Publication Date(Web):August 2013
DOI:10.1016/j.cclet.2013.05.001
Hierarchical flower-like architectures of [Ni3(BTC)2·12H2O] (BTC3− = benzene-1,3,5-tricarboxylate) were successfully prepared by a simple solution-phase method under mild conditions without any template or surfactant. Phase-pure porous NiO nanocrystals were obtained by annealing the Ni-BTC complex without significant alteration in morphology. The product was characterized by X-ray diffraction techniques, field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high-resolution TEM (HRTEM). The catalytic effect of the NiO product was investigated on the thermal decomposition of ammonium perchlorate (AP) and it was found that the annealed NiO product has higher catalytic activity than the commercial NiO.Porous NiO superstructures are obtained by annealing the hierarchical flower-like architectures of [Ni3(BTC)2·12H2O] prepared by a simple solution-phase method under mild conditions, and show good catalytic property for the decomposition of ammonium perchlorate.
Co-reporter:Peng Wang, Taka-aki Okamura, Hong-Ping Zhou, Wei-Yin Sun, Yu-Peng Tian
Chinese Chemical Letters 2013 Volume 24(Issue 1) pp:20-22
Publication Date(Web):January 2013
DOI:10.1016/j.cclet.2012.12.010
A new metal complex [MnL2](NO3)2·CH3CN (1) was synthesized by reaction of 4′-4-(1,2,4-triazol-1-yl)-phenyl-2,2′:6′,2″-terpyridine (L) with manganese nitrate. The structure of the complex was determined by X-ray crystallography. The results of UV–vis studies showed that the complex exhibits colorimetric sensing ability for Fe3+, which can be observed by naked eye.A terpyridine-based Mn(II) complex shows apparent color change upon addition of Fe(III), which can be detected by naked eye.
Co-reporter:Li-Na Jin, Qing Liu, Wei-Yin Sun
Solid State Sciences 2013 Volume 19() pp:45-50
Publication Date(Web):May 2013
DOI:10.1016/j.solidstatesciences.2013.02.013
Uniform octahedral gadolinium vanadate (GdVO4) microcrystals were successfully prepared by a simple hydrothermal route in two-steps. Firstly, homogenous Gd2(CO3)3·xH2O nanospheres with an average diameter of ∼80 nm were synthesized by using a facile hydrothermal method. Then, uniform octahedral GdVO4 microcrystals were obtained at the expense of the precursor during a hydrothermal conversion process. The results show that the morphology of the as-synthesized GdVO4 crystals could gradually evolve with prolonging the reaction time. Also, it was found that the reaction pH played an important role in the formation of octahedral GdVO4 microcrystals. A possible formation mechanism of octahedral GdVO4 microcrystals was discussed. The as-obtained Eu3+-doped GdVO4 products showed strong characteristic red emission under the ultraviolet excitation, which might find potential applications in the fields of fluorescent lamps, display systems and optoelectronic devices.Graphical abstractHighlights► Octahedral GdVO4 microcrystals were synthesized via a two-step hydrothermal route. ► A dissolution–recrystallization mechanism was proposed. ► GdVO4:Eu3+ octahedral microcrystals show strong photoluminescence.
Co-reporter:Gao-Chao Lv, Yue Zhao, Jian Fan, Shui-Sheng Chen, Zhi Su, Wei-Yin Sun
Inorganic Chemistry Communications 2013 Volume 36() pp:59-62
Publication Date(Web):October 2013
DOI:10.1016/j.inoche.2013.08.009
Highlights•Two-dimensional coordination networks with kgd topology were prepared.•The networks exhibit different stacking modes between the adjacent layers.•Fluorescence and magnetic properties of the complexes were studied.Three new Mn(II) and Cd(II) coordination polymers with kgd network topology, namely, [Mn3(T4)2(DEF)6] · 2H2O (1), [Mn3(T4)2(DMSO)2(CH3OH)4] · 2CH3OH · 3H2O (2) and [Cd3(T4)2(DMF)6] · 5CH3OH · 3DMF · H2O (3), have been prepared by reactions of tris[4-(1H-tetrazol-5-yl)phenyl]amine (H3T4) with corresponding metal salt and characterized by single crystal and powder X-ray diffractions, IR and thermogravimetric analyses. In compounds 1 and 3, the layers adopt center to center stacking, while there is a slight shifting between the adjacent layers in compound 2. Complexes 1 and 2 exhibit overall weak antiferromagnetic coupling between the neighboring Mn(II) atoms, and compound 3 shows luminescent property in the solid state at room temperature.Three new Mn(II) and Cd(II) coordination networks with kgd topology, namely, [Mn3(T4)2(DEF)6] · 2H2O (1), [Mn3(T4)2(DMSO)2(CH3OH)4] · 2CH3OH · 3H2O (2) and [Cd3(T4)2(DMF)6] · 5CH3OH · 3DMF · H2O (3), have been prepared by reactions of tris[4-(1H-tetrazol-5-yl)phenyl]amine (H3T4) with corresponding metal salt and characterized.
Co-reporter:Li-Na Jin, Qing Liu, Wei-Yin Sun
Materials Letters 2013 Volumes 102–103() pp:112-115
Publication Date(Web):July 2013
DOI:10.1016/j.matlet.2013.03.127
•Porous yolk-shell structured In2O3.•Indium(III) benzophenone-4,4′-dicarboxylate sub-microspheres as precursors.•Raman and photoluminescence spectra of the In2O3.Porous yolk-shell In2O3 was successfully prepared via a two-step method. Indium(III) benzophenone-4,4′-dicarboxylate (In-BPnDC) sub-microspheres with an average diameter of ~250 nm were first obtained on a large scale via a simple solution reaction. Then, porous yolk-shell structured In2O3 particles were prepared by annealing In-BPnDC complexes. The products were characterized by X-ray diffraction, field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high-resolution TEM (HRTEM). The as-obtained In2O3 showed a BET specific surface area of 33.17 m2/g and a mesoporous structure according to nitrogen adsorption–desorption experiments. In addition, the Raman spectra and room-temperature photoluminescence of In2O3yolk-shell structures were also studied.Graphical abstract
Co-reporter:Qing Liu, Li-Na Jin and Wei-Yin Sun
Chemical Communications 2012 vol. 48(Issue 70) pp:8814-8816
Publication Date(Web):16 Jul 2012
DOI:10.1039/C2CC34192A
A porous coordination polymer [Cu3(btc)2] with controllable size and morphology from nanocube to microoctahedron was readily synthesized in an ethanol–water mixture at room temperature by adjusting the concentration of the surfactant and the polymer shows size- and morphology-dependent sorption properties.
Co-reporter:Gao-Chao Lv, Peng Wang, Qing Liu, Jian Fan, Kai Chen and Wei-Yin Sun
Chemical Communications 2012 vol. 48(Issue 82) pp:10249-10251
Publication Date(Web):12 Sep 2012
DOI:10.1039/C2CC35456J
A series of Cu(II) complexes showed unprecedented reversible cascades of single-crystal-to-single-crystal (SCSC) transformations, and more interestingly, very rapid crystal dynamic processes were observed in this system via the substitution of coordinating components without loss of single crystallinity.
Co-reporter:Chao Hou ; Qing Liu ; Jian Fan ; Yue Zhao ; Peng Wang
Inorganic Chemistry 2012 Volume 51(Issue 15) pp:8402-8408
Publication Date(Web):July 17, 2012
DOI:10.1021/ic300950h
A microporous and noninterpenetrated metal–organic framework [Cu3(L)2(DABCO)(H2O)]·15H2O·9DMF (1) has been synthesized using two different ligands, [1,1′:3′,1″-terphenyl]-4,4″,5′-tricarboxylic acid (H3L) and 1,4-diazabicyclo[2.2.2]octane (DABCO). As revealed by variable-temperature powder X-ray diffraction (VT-PXRD) measurements, N,N′-ditopic DABCO plays an important role for stabilization of the Cu–L framework. The three-dimensional framework of 1 exhibits high stability and excellent adsorption capacity for H2 (54.3 mg g–1 at 77 K and 20 bar), CO2 (871 mg g–1 at 298 K and 20 bar), CH4 (116.7 mg g–1, 99 cm3 (STP) cm–3 at 298 K and 20 bar), and n-pentane (686 mg g–1 at 298 K and 1 bar). Interestingly, the excellent selectivity toward CO2 over N2 at ambient temperature (273 and 298 K) and 1 bar makes complex 1 possess practical application in gas separation and purification.
Co-reporter:Li-Na Jin, Qing Liu, Yi Lu and Wei-Yin Sun
CrystEngComm 2012 vol. 14(Issue 10) pp:3515-3520
Publication Date(Web):09 Mar 2012
DOI:10.1039/C2CE25075F
Well-dispersed hierarchical straw–sheaf-like architectures of [Gd(1,4-BDC)1.5(H2O)2] (BDC2− = benzene-1,4-dicarboxylate) have been successfully synthesized via an ultrasonic-assisted solution-phase method in the presence of polyvinylpyrrolidone (PVP, 30 K). The as-obtained products were characterized by X-ray powder diffraction (XRD), energy dispersive spectrometry (EDS), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). Systematic investigations have been performed on the factors influencing the morphology of [Gd(1,4-BDC)1.5(H2O)2] nanostructures, such as the concentration of Na2BDC and Gd(NO3)3·6H2O, the ultrasonic time and power, as well as the amount of PVP. A possible mechanism responsible for the formation of hierarchical architectures was proposed. The as-obtained Eu3+- and Tb3+-doped [Gd(1,4-BDC)1.5(H2O)2] products show strong characteristic red and green emissions under ultraviolet excitation. Furthermore, the straw–sheaf shaped Gd2O3 can be obtained via a thermal decomposition method using the Gd-1,4-BDC complex as a precursor.
Co-reporter:Shui-Sheng Chen, Yue Zhao, Jian Fan, Taka-aki Okamura, Zheng-Shuai Bai, Zhi-Hao Chen and Wei-Yin Sun
CrystEngComm 2012 vol. 14(Issue 10) pp:3564-3576
Publication Date(Web):12 Mar 2012
DOI:10.1039/C2CE06632G
Nine new coordination polymers [Mn(L)(OX)] (1), [Zn(L)(MBDC)] (2), [Zn(L)(BPDA)] (3), [Co3(L)2(BTA)2]·2H2O (4), [Co2(L)2(BTCA)]·2H2O (5), [Ni(L)(e,a-cis-1,2-CHDC)]·2H2O (6), [Co(L)(e,a-cis-1,4-CHDC)] (7), [Co(L)(e,e-trans-1,4-CHDC)]·2H2O (8) and [Co(L)(e,e,e-cis-1,3,5-HCHTC)]·0.45H2O (9) were obtained by reactions of varied metal salts with 1,4-di(1H-imidazol-4-yl)benzene (L) in the presence of corresponding auxiliary ligands of oxalic acid (H2OX), 5-methyl-1,3-benzenedicarboxylic acid (H2MBDC), 4,4′-biphenyldicarboxylic acid (H2BPDA), benzene-1,3,5-triacetic acid (H3BTA), 1,2,4,5-benzenetetracarboxylic acid (H4BTCA), cis-1,2-cyclohexanedicarboxylic acid (cis-1,2-H2CHDC), cis-/trans-1,4-cyclohexanedicarboxylic acid (cis-/trans-1,4-H2CHDC) and cis-1,3,5-cyclohexane tricarboxylic acid (cis-1,3,5-H3CHTC), respectively. Complex 1 has a one-dimensional (1D) chain structure and 2 has a two-dimensional (2D) network with 63-hcb topology. Complex 3 is a complicated uninodal 4-connected three-dimensional (3D) net with Point (Schläfli) symbol (4·6·83·10)(4·63·82)(63·103)(64·82) while 4 is a (3,8)-connected tfz-d 3D net with Point (Schläfli) symbol (43)2(46·618·84) based on the trinuclear Co(II) secondary building units (SBUs). Complex 5 is a 3-fold interpenetrating mog net with Point (Schläfli) symbol of (4·64·8)2(42·62·82), while 6 is a 2D net with (4,4) topology based on binuclear SBUs. In contrast to the 2D network of 7 with e,a-cis-1,4-CHDC2−, 8 with e,e-trans-1,4-CHDC2− is a 5-fold interpenetrating 66-dia 3D net. Complex 9 has a 1D ladder-like chain structure with a stable conformation from the e,e,e-cis-1,3,5-HCHTC2− ligand. Complexes 2 and 3 exhibit intense light blue emission in the solid state at room temperature and the results of magnetic measurements showed that there are antiferromagnetic interactions in 1.
Co-reporter:Hai-Wei Kuai, Jian Fan, Qing Liu and Wei-Yin Sun
CrystEngComm 2012 vol. 14(Issue 10) pp:3708-3716
Publication Date(Web):12 Mar 2012
DOI:10.1039/C2CE25062D
Three cadmium–organic frameworks [Cd(L)(DMF)(H2O)]·H2O (1), [Cd(L)(H2O)2]2·5H2O (2) and [Cd2(L)2(H2O)2]2·H2O (3) and two zinc complexes [Zn(L)] (4) and [Zn(L)(H2O)] (5) [H2L = 5-(imidazol-1-ylmethyl)isophthalic acid, DMF = N,N-dimethylformamide] have been synthesized and characterized by single crystal X-ray structure determination, IR, elemental analysis, and powder X-ray diffraction. Both these two series of complexes exhibit structural diversity, which was controlled by non-innocent alkaline reagents. Within the cadmium series, the in situ generated dimethylamine from DMF, NaOH and carbonate salt were utilized as the basic reagents for the syntheses of 1, 2 and 3, respectively. As a result, 1 has a 1D ladder structure, 2 is a uninodal 3-connected 2D (63) network and 3 displays a binodal (3,6)-connected 3D framework with (4.62)2(42.610.83) topology. Within the zinc series, tetrabutylammonium hydroxide and carbonate salt were used for the syntheses of 4 and 5, respectively. 4 showed a binodal (3,6)-connected 2D kgd net with [(43)2(46.66.83)] topology; while 5 is a 2-fold interpenetrated 3D (10, 3)-a architecture. The adsorption and luminescent properties of the complexes were investigated.
Co-reporter:Min Chen, Yi Lu, Jian Fan, Gao-Chao Lv, Yue Zhao, Yan Zhang and Wei-Yin Sun
CrystEngComm 2012 vol. 14(Issue 6) pp:2015-2023
Publication Date(Web):11 Jan 2012
DOI:10.1039/C1CE06456H
Five zinc(II) coordination polymers with 5-(4H-1,2,4-triazol-4-yl)benzene-1,3-dicarboxylic acid (H2L), {[Zn2(L)2(H2O)4]·3H2O}n (1), {[Zn2(L)2(H2O)2]·3H2O}n (2), [Zn(L)(H2O)]n (3), [Zn(L)(H2O)]n (4) and {[Zn10(L)8(μ3-O)2(H2O)6]·8H2O}n (5), have been synthesized and structurally characterized. The compounds exhibit unprecedentedly high structural diversity. 1, 2, 3 and 5 are obtained by temperature-dependent synthesis and 4 is selectively induced by addition of 1,3,5-benzenetricarboxylic acid. In 1, the two-dimensional (2D) layers are further linked together by hydrogen bonds to form a three-dimensional (3D) supramolecular framework. 2 displays a non-interpenetrating (4,5)-connected 3D framework, while 3 and 4 present a pair of pseudopolymorphs with different interpenetrating structures. 3 is a two-fold interpenetrating hcb architecture while 4 shows a self-interpenetrating 3D msw-4-C2/c net. The results suggest that reaction temperature and auxiliary ligand play an important role to determine the resulting structures in this system. Furthermore, the photoluminescent, nonlinear optical and ferroelectric properties of the compounds were investigated.
Co-reporter:Li-Na Jin, Qing Liu and Wei-Yin Sun
CrystEngComm 2012 vol. 14(Issue 22) pp:7721-7726
Publication Date(Web):03 Jul 2012
DOI:10.1039/C2CE25713K
In this paper, we report a facile approach for the shape-controlled synthesis of cobalt(II)-based coordination polymer particles. Three different structures of flower-like architectures, multilayer stacked structures and nanosheets have been synthesized by varying the volume ratio of ethanol and water. Phase-pure Co3O4 nanocrystals have been obtained by annealing the coordination polymer particles without significant alterations in morphology. The products have been characterized by X-ray diffraction techniques, field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and high-resolution TEM (HRTEM). The catalytic effect was investigated for the Co3O4 nanocrystals with different morphology on the thermal decomposition of ammonium perchlorate (AP) and it was found that the Co3O4 nanosheet has the highest catalytic activity. The surface areas of Co3O4 nanocrystals are measured by the Brunauer–Emmett–Teller (BET) technique and the results show that the catalytic activity of Co3O4 nanocrystals for the thermal decomposition of AP increases with the increase of BET surface area and pore volume.
Co-reporter:Chao Hou, Qing Liu, Taka-aki Okamura, Peng Wang and Wei-Yin Sun
CrystEngComm 2012 vol. 14(Issue 24) pp:8569-8576
Publication Date(Web):11 Oct 2012
DOI:10.1039/C2CE26533H
Three new porous metal–organic frameworks {[Co(L)(PIN)]·dioxane·H2O}n (1), {[Co(L)(DPE)]·0.5DPE}n (2) and {[Co(L)(BPE)]·4H2O}n (3) with the same 2-fold interpenetrating hms topology based on 5-(pyridin-4-yl)isophthalate (L2−) and different pillar ligands of N-(4-pyridyl)isonicotinamide (PIN), 1,2-di(4-pyridyl)ethylene (DPE) and 1,2-bis(4-pyridyl)ethane (BPE) have been prepared and characterized by IR, thermogravimetric analysis, single crystal and powder X-ray diffractions. Interestingly, 1 possesses a flexible framework upon desolvation and H2O/MeOH/EtOH vapor adsorption, and the desolvated sample exhibits a stepwise uptake of CO2 (195 K), H2O (298 K) and MeOH (298 K). More importantly, the desolvated 1 shows high enthalpy of CO2 adsorption and high selectivity for CO2 over N2 as well as H2O/MeOH over EtOH at 298 K.
Co-reporter:Min Chen, Zheng-Shuai Bai, Qing Liu, Taka-aki Okamura, Yi Lu and Wei-Yin Sun
CrystEngComm 2012 vol. 14(Issue 24) pp:8642-8648
Publication Date(Web):11 Oct 2012
DOI:10.1039/C2CE26338F
Three new coordination polymers [Mn4(bptca)2(titmb)(H2O)7]·DMF·4H2O (1), [Ni2(bptca)(titmb)2]·13H2O (2) and [Co2(bptca)(titmb)2]·13H2O (3) were constructed from 4,4′-bipyridine-2,2′,6,6′-tetracarboxylic acid (H4bptca) and 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) under hydrothermal conditions. Single crystal X-ray diffraction analysis shows that 1 contains [Mn4(μ2-OCO)4] subunits linked through organic ligands to form a two-dimensional (2D) double-layer structure, while 2 and 3 are isostructural and exhibit a unique three-dimensional (3D) framework with open channels resided by water molecules. The magnetic behavior of 1 and sorption property of 2 have been investigated.
Co-reporter:Shui-Sheng Chen, Zhi-Hao Chen, Jian Fan, Taka-aki Okamura, Zheng-Shuai Bai, Mei-Fang Lv, and Wei-Yin Sun
Crystal Growth & Design 2012 Volume 12(Issue 5) pp:2315-2326
Publication Date(Web):March 29, 2012
DOI:10.1021/cg2016275
Six new metal–organic coordination polymers [Mn(H3L)(ox)]·H2O (1), [Zn2(H2L)(pbdc)(μ2-OH)]·2H2O (2), [Co(H3L)(obea)]·3H2O (3), [Ni(H3L)(pbea)] (4), [Co(H3L)(pbea)(H2O)2] (5), and [Co4(H2L)2(pbea)3] (6) were synthesized by reactions of the corresponding metal salt with rigid tripodal ligand 1,3,5-tri(1H-imidazol-4-yl)benzene (H3L) and different dicarboxylic acid of oxalic acid (H2ox), 1,4-benzenedicarboxylic acid (H2pbdc), 1,2-phenylenediacetic acid (H2obea), 1,4-phenylenediacetic acid (H2pbea), respectively. The results of X-ray crystallographic analysis indicate that 1 and 3 are two-dimensional (2D) networks with 63-hcb topology, while 2 is (4,5)-connected three-dimensional (3D) net with Point (Schläfli) symbol of (42·52·72)(42·53·74·8). Complex 4 is a binodal (3,4)-connected 2D network with V2O5-type topology. Complexes 5 and 6 were obtained through controlling reaction temperature, 5 features a one-dimensional (1D) chain, whereas 6 is an unprecedented tetra-nodal (3,4)-connected 3D net with Point (Schläfli) symbol of (4·62·103)(4·62)(4·64·8)2 attributable to the rich coordination modes of the ligands. The results of magnetic measurements showed that there are antiferromagnetic interactions in 1. Complex 2 exhibits intense light blue emission in the solid state at room temperature, while 3 shows water vapor adsorption property.
Co-reporter:Li Luo, Peng Wang, Guan-Cheng Xu, Qing Liu, Kai Chen, Yi Lu, Yue Zhao, and Wei-Yin Sun
Crystal Growth & Design 2012 Volume 12(Issue 5) pp:2634-2645
Publication Date(Web):April 2, 2012
DOI:10.1021/cg300220q
Six new coordination polymers [Zn(L)0.5(CO3)]·H2O (1), [Zn(L)0.5(DC)]·H2O (2), [Cd(L)0.5(DC)] (3), [Cd(L)0.5(PBEA)]·H2O (4), [Cd2(L)(MBEA)2]·4H2O (5), and [Zn(L)0.5(MBEA)]·2H2O (6) with different structures and topologies were successfully synthesized by hydrothermal reactions of zinc(II)/cadmium(II) salts with rigid ligand 3,3′,5,5′-tetra(1H-imidazol-1-yl)-1,1′-biphenyl (L) and auxiliary multicarboxylic acids of 1,3,5-tri(4-carboxyphenyl)benzene (H3BTB), 1,4-benzenediacrylic acid (H2DC), 1,4-benzenediacetic acid (H2PBEA), and 1,3-benzenediacetic acid (H2MBEA), respectively. Carbonate anion, rather than the carboxylate anion of H3BTB, is incorporated in 1. Complexes 1 and 5 are (4,4)- and (4,6)-connected binodal two-dimensional (2D) networks with a point (Schläfli) symbol of (4.64.8)2(42.64) and (32.42.52)(34.44.54.63), respectively. Complex 2 is a self-penetrating three-dimensional (3D) framework with a point (Schläfli) symbol of (62.84)(64.82)2, while 3 shows a (3,4,5)-connected trinodal 3D framework with a point (Schläfli) symbol of (4.63.86)2(42.84)(63)2. The 3-fold interpenetrating net of 4 is a subnet of sta with a point (Schläfli) symbol of (4.64.8)2(42.62.82), while the net of 6 is vested in nbo set net with a point (Schläfli) symbol of (64)(82). The results show that the auxiliary ligands and metal centers play important roles in the formation of complexes with diverse structures. Furthermore, the thermal stability, photoluminescence, and sorption properties of the complexes were investigated.
Co-reporter:Yue Zhao, Xin Zhou, Taka-aki Okamura, Min Chen, Yi Lu, Wei-Yin Sun and Jin-Quan Yu
Dalton Transactions 2012 vol. 41(Issue 19) pp:5889-5896
Publication Date(Web):08 Mar 2012
DOI:10.1039/C2DT30134B
A novel supramolecular complex [Ag(L)(NO3)] (1) was synthesized by reaction of the oxazoline-containing ligand 1,4-bis(4,5-dihydro-2-oxazolyl)benzene (L) with silver(I) nitrate and its structure was determined by single-crystal X-ray diffraction. Structurally speaking, the one-dimensional (1D) zigzag chains of 1, in which the Ag(I) is three-coordinated with distorted trigonal-planar coordination geometry, are linked together by the hydrogen bonding interactions to form a three-dimensional (3D) supramolecular structure. It was found that the silver supramolecule 1 catalyzes the three-component coupling reactions of aldehyde, alkyne, and amine in the air at room temperature to generate propargylic amines with high efficiency. No additional co-catalyst or activator is required. A variety of aldehydes and amines were used to demonstrate the versatility of the reaction.
Co-reporter:Chao Hou, Qing Liu, Yi Lu, Taka-aki Okamura, Peng Wang, Min Chen, Wei-Yin Sun
Microporous and Mesoporous Materials 2012 Volume 152() pp:96-103
Publication Date(Web):1 April 2012
DOI:10.1016/j.micromeso.2011.11.058
Three novel metal-organic frameworks based on the N-(4-pyridylmethyl)iminodiacetate (pmida2−), namely {[Cd(pmida)H2O]·1.8 H2O]}n (1), {[Cd(pmida)(H2O)]·2H2O}n·(2) and {[Zn(pmida)(H2O)]·2H2O}n (3), have been prepared and characterized by single crystal X-ray diffraction, IR, powder X-ray diffraction (PXRD) and thermogravimetric analyses. Complex 1 has a unique irl topology and is a 3D framework with 1D open channels, whereas complexes 2 and 3 are isostructural 3D net with dia topology. Interestingly, complexes 1 and 2 obtained by the same reaction are supramolecular isomers with different 3D structures and topologies. Second-order non-linear optical (NLO) effect of the complexes, ferroelectric property of 1 as well as sorption properties of 1 and 3 were investigated.Graphical abstractHighlights► Three-dimensional coordination frameworks with different structures and topologies. ► Selective sorption behavior of H2O, MeOH over N2, EtOH. ► Second-order non-linear optical effect and ferroelectric property.
Co-reporter:Peng Wang, Zheng Li, Gao-Chao Lv, Hong-Ping Zhou, Chao Hou, Wei-Yin Sun, Yu-Peng Tian
Inorganic Chemistry Communications 2012 Volume 18() pp:87-91
Publication Date(Web):April 2012
DOI:10.1016/j.inoche.2012.01.024
A new terpyridine derivative ligand 4′-4-(1,2,4-triazol-1-yl)-phenyl-2,2′:6′,2″-terpyridine (L) was prepared and its metal complex [Zn(L)2](NO3)2·H2O (1) was obtained by reaction of L with zinc(II) nitrate hexahydrate. The structure of the complex was determined by X-ray crystallography. The fluorescent spectral measurements revealed that complex 1 is a selective fluorescent sensor for Co2 + and Ni2 + ions but not for metal ions such as Mg2 +, Pb2 +, Cu2 +, Fe2 +, In3 +, Zn2 +, Cd2 + and Fe3 +. Furthermore, EDTA (ethylene diamine tetraacetic acid) can selectively turn on the quenched fluorescence of complex 1 induced by Co2 + (“on–off–on” type sensor) but cannot turn on the one induced by Ni2 + (“on–off” type sensor).A Zn(II) complex [Zn(L)2](NO3)2·H2O (1) with terpyridine derivative ligand 4′-4-(1,2,4-triazol-1-yl)-phenyl-2,2′:6′,2″-terpyridine (L) was found to be a “on–off–on” type fluorescence sensor for Co2 + and “on–off” type for Ni2 +.Highlights► Zinc(II) complex with terpyridine derivative ligand. ► A selective fluorescence sensor. ► “on–off” type probe for cobalt(II) and nickel(II) ions.
Co-reporter:Yue Zhao, Ling-Ling Zhai, Gao-Chao Lv, Xin Zhou, Wei-Yin Sun
Inorganica Chimica Acta 2012 Volume 392() pp:38-45
Publication Date(Web):30 September 2012
DOI:10.1016/j.ica.2012.06.035
Six new coordination complexes [Ag2(L)2](NO3)2 (1), [Ag2(L)2](ClO4)2 (2), [Ag3(L)4](SbF6)3 (3), [Ag2(L)2(CH3CN)2](PF6)2 (4), [Ag2(L)2(SO3CH3)2](CH3OH)2 (5) and [Ag2(L)2(SO3CF3)2] (6) were successfully synthesized by reactions of 1,3-bis(2-oxazolinyl)benzene (L) with different Ag(I) salts under the same reaction conditions. Complexes 1 and 2 have the same 16-membered ring structures, which are extended by Ag···O weak interactions and hydrogen bonds to form 3D frameworks. Complex 3 containing two- and four-coordinated Ag(I) atoms has two inter-connected 16-membered rings which are linked together by SbF6- to form a 3D framework. In complex 4, the Ag(I) is three-coordinated by two N atoms from the L ligands and one N atom from acetonitrile solvent and the structure of 4 is also a 16-membered ring. Complexes 5 and 6 have similar 16-member ring structure, and the anions coordinate with Ag(I) atoms. The results reveal that anions can influence on the structure of the complexes. Furthermore, the complexes were characterized by electrospray mass spectrometry.Graphical abstractSix new Ag(I) complexes with oxazoline-containing bidentate ligand have been synthesized and the influence of counteranions was discussed. The electrospray mass spectrometry of the complexes were investigated.Highlights► Silver(I) complexes with oxazoline-containing ligand. ► Complexes with bi- and trinuclear structures. ► Electrospray mass spectrometry of the complexes.
Co-reporter:Zhi Su, Gao-Chao Lv, Jian Fan, Guang-Xiang Liu, Wei-Yin Sun
Inorganic Chemistry Communications 2012 Volume 15() pp:317-320
Publication Date(Web):January 2012
DOI:10.1016/j.inoche.2011.11.015
Two three-dimensional (3D) chiral frameworks, [Cd6(L)4(d-Cam)4(H2O)4]·2H2O (1D) and [Cd6(L)4(l-Cam)4(H2O)4]·2H2O (1L) [HL = 3,5-di(imidazol-1-yl)benzoic acid, d-H2Cam = d-camphoric acid, l-H2Cam = l-camphoric acid], have been synthesized under hydrothermal conditions, which represent a nice example of enantioselectivity of organic racemic ligands (dl-camphorates) during the self-assembly process and formation of the metal complexes. Compounds 1D and 1L feature 3D framework with chiral chains constructed by Cd(II) cations and camphorate anions. Solid-state circular dichroism (CD) spectra of 1D and 1L revealed that they are enantiomers. Furthermore, the complex with chiral C2 space group displays ferroelectric behavior with a remnant electric polarization (Pr) of ~ 0.140 μC/cm2 and an electric coercive field (Ec) of ~ 17.11 kV/cm.Racemic camphorates (dl-Cam2 −) were resolved into two homochiral enantomers in the formation of three-dimensional Cd(II) frameworks with 3,5-di(imidazol-1-yl)benzoate, which provide a nice example of resolution of dl-H2Cam without chiral template.Highlights► Homochiral three-dimensional cadmium(II) framework. ► Complex with camphoric acid and 3,5-di(imidazol-1-yl)benzoic acid. ► SHG and ferroelectric property of the complex.
Co-reporter:Zhi Su;Jian Fan;Taka-aki Okamura;Weiyin Sun
Chinese Journal of Chemistry 2012 Volume 30( Issue 9) pp:2016-2022
Publication Date(Web):
DOI:10.1002/cjoc.201200715
Abstract
Three new metal-organic frameworks (MOFs), namely [Zn(tib)(PDC)] (1), [Zn3(tib)2(CHDC)3]·8H2O (2) and [Zn3(tib)2(BTC)2]·4.95H2O (3) were synthesized by hydrothermal reactions of ZnCl2 with 1,3,5-tris(1-imidazolyl)benzene (tib) and different carboxylate ligands of 2,6-pyridinedicarboxylic acid (H2PDC), 1,4-cyclohexanedicarboxylic acid (H2CHDC) and 1,3,5-benzenetriacetic acid (H3BTC), respectively. The complexes were characterized by IR, thermogravimetric analysis, single crystal and powder X-ray diffractions. Complex 1 has a binuclear structure, in which one imidazole group of tib is free of coordination, while 2 has three-dimensional (3D) framework with the CHDC-Zn microcycles filled into the tib-Zn 3D net, and 3 is a 2-fold interpenetrating 3D framework with the interconnection of two one-dimensional (1D) chains formed by BTC-Zn and tib-Zn, respectively. The different structures of 1–3 are resulted from the distinct carboxylate ligands. In addition, complexes 1–3 show obvious emissions at room temperature in the solid state.
Co-reporter:Yue Zhao, Ling-Ling Zhai, Jian Fan, Kai Chen, Wei-Yin Sun
Polyhedron 2012 46(1) pp: 16-24
Publication Date(Web):
DOI:10.1016/j.poly.2012.07.079
Co-reporter:Peng Wang, Li Luo, Taka-aki Okamura, Hong-Ping Zhou, Wei-Yin Sun, Yu-Peng Tian
Polyhedron 2012 44(1) pp: 18-27
Publication Date(Web):
DOI:10.1016/j.poly.2012.05.047
Co-reporter:Chao Hou, Yue Zhao, Yi Lu, Peng Wang, Wei-Yin Sun
Inorganic Chemistry Communications 2012 20() pp: 317-321
Publication Date(Web):
DOI:10.1016/j.inoche.2012.03.039
Co-reporter:Li Luo, Yue Zhao, Yi Lu, Taka-aki Okamura, Wei-Yin Sun
Polyhedron 2012 Volume 38(Issue 1) pp:88-96
Publication Date(Web):11 May 2012
DOI:10.1016/j.poly.2012.02.027
Six new coordination polymers, [Cu(L)2(H2O)2](NO3)2 (1), [Cu(L)2](ClO4)2 (2), [Cd(L)2(H2O)2](ClO4)2 (3), [Cd(L)(OAc)2(H2O)] (4), [Cu3(L)4(H2O)2(SO4)](SO4)2·30H2O (5), and [Ni(L)(H2O)3(SO4)] (6) [L = 3,5-di(1H-imidazol-1-yl)pyridine, OAc− = CH3COO−], have been prepared and characterized by X-ray diffraction, IR, elemental and thermogravimetric analyses. Complexes 1, 4 and 6 have different one-dimensional (1D) chain structures, while 2 and 4 are two-dimensional (2D) networks. The chains and layers are further linked together by hydrogen bonds to generate three-dimensional (3D) frameworks. Complex 5 is a (3,4,4)-connected 3D framework with a Point (Schläfli) symbol of (4.82)4(4.83.102)2(42.82.102). The influences of the coordination modes of the ligand L, metal center as well as the counteranion on the structures of the complexes are discussed. Furthermore, the reversible anion exchange property of 3 and the photoluminescence properties of 3 and 4 have been investigated.Graphical abstractSix new coordination polymers with the 3,5-di(1H-imidazol-1-yl)pyridine ligand and different metal centers have been prepared and characterized by X-ray diffraction, IR, elemental and thermogravimetric analyses. The complexes show diverse 1D, 2D and 3D structures. The reversible anion exchange and photoluminescence properties of the complexes were investigated.Highlights► Coordination framework. ► Complexes with the 3,5-di(1H-imidazol-1-yl)pyridine ligand. ► Anion exchange and photoluminescence properties of the complexes.
Co-reporter:Shui-Sheng Chen, Min Chen, Satoshi Takamizawa, Man-Sheng Chen, Zhi Su and Wei-Yin Sun
Chemical Communications 2011 vol. 47(Issue 2) pp:752-754
Publication Date(Web):11 Nov 2010
DOI:10.1039/C0CC04085A
A highly stable copper(II) microporous framework with cylindrical channels constructed from 1,4-di(1H-imidazol-4-yl)benzene (H2L) and CuCl2·2H2O is composed of Cu(II)-imidazolate tubes interconnected by the 1,4-phenylene group of L2−, and shows temperature dependent selective gas sorption properties.
Co-reporter:Man-Sheng Chen, Min Chen, Satoshi Takamizawa, Taka-aki Okamura, Jian Fan and Wei-Yin Sun
Chemical Communications 2011 vol. 47(Issue 13) pp:3787-3789
Publication Date(Web):02 Feb 2011
DOI:10.1039/C0CC04689B
A unique 4-fold interpenetrated (10,3)-b copper(II) framework exhibits reversible dehydration and rehydration in a single-crystal-to-single-crystal (SC–SC) process, and the dehydrated material can encapsulate CH3OH molecules, again in a SC–SC fashion, and shows selective adsorption of H2 and CO2 over N2.
Co-reporter:Shui-Sheng Chen, Min Chen, Satoshi Takamizawa, Peng Wang, Gao-Chao Lv and Wei-Yin Sun
Chemical Communications 2011 vol. 47(Issue 17) pp:4902-4904
Publication Date(Web):25 Mar 2011
DOI:10.1039/C1CC10899A
Two porous supramolecular isomeric frameworks show unique sorption properties, one with temperature dependent stepwise and hysteretic selective sorption of CO2 while the other one shows gas uptake capacity for CO2, N2, H2 and CH4 at low temperature and selective sorption of CO2 over N2 around room temperature.
Co-reporter:Zhi Su ; Min Chen ; Taka-aki Okamura ; Man-Sheng Chen ; Shui-Sheng Chen
Inorganic Chemistry 2011 Volume 50(Issue 3) pp:985-991
Publication Date(Web):January 10, 2011
DOI:10.1021/ic101618n
A three-dimensional (3D) coordination polymer, [Co3(L)2(BTEC)(H2O)2]·2H2O [1, HL = 3,5-di(imidazol-1-yl)benzoic acid, H4BTEC = 1,2,4,5-benzenetetracarboxylic acid], with tfz-d topology has been hydrothermally synthesized. The framework of 1 has high thermal stability and exhibits single-crystal-to-single-crystal (SCSC) transformations upon removing and rebinding the noncoordinated and coordinated water molecules. X-ray crystallographic analyses revealed that the coordination geometry of Co(II) changes from octahedral to square pyramid upon dehydration, accompanying the appearance of one-dimensional (1D) open channels with dimensions of 2.0 × 2.8 Å. The dehydrated form [Co3(L)2(BTEC)] (2) exhibits highly selective adsorption of water molecules over N2, CH3OH, and CH3CH2OH, which could be used as sensors for water molecules. Furthermore, the magnetic properties of 1 and 2 were investigated, showing the existence of ferromagnetic interaction between the Co(II) atoms within the trinuclear subunit.
Co-reporter:Zhi Su, Jian Fan, Min Chen, Taka-aki Okamura, and Wei-Yin Sun
Crystal Growth & Design 2011 Volume 11(Issue 4) pp:1159
Publication Date(Web):February 8, 2011
DOI:10.1021/cg101365v
Six new coordination polymers, namely, [Cd3(L)2(dpa)2(H2O)] (1), [Co3(L)2(dpa)2(H2O)2]·H2O (2), [Cd(L)(chda)0.5] (3), [Cd(L)(dc)0.5(H2O)] (4), [Cd2(L)2(cca)]·2H2O (5), and [Cd2(L)2(cppa)]·2H2O (6) [HL = 3,5-di(imidazol-1-yl)benzoic acid, H2dpa = diphenic acid, H2chda = 1,4-cyclohexanedicarboxylic acid, H2dc = 1,4-benzenediacrylic acid, H2cca = 4-carboxycinnamic acid, H2cppa = 3-(4-carboxyphenyl)propionic acid] have been obtained under hydrothermal conditions. Complexes 1 and 2 are novel (3,6)-connected three-dimensional (3D) frameworks based on trinuclear subunits. Complex 3 shows a rare 4-fold interpenetrating 3D dmc net, and 4 features a uninodal 6-connected 3D self-penetrating framework. Both 5 and 6 possess unusual 3-fold interpenetrating 3D (3,4)-connected InS nets. In 1−6 each metal atom is coordinated by the combination of L− and auxiliary carboxylate ligands. In 1 and 2 the auxiliary carboxylate ligand plays an important role in the formation of metal cluster based subunits. In 3−6 the auxiliary carboxylate ligands pillar the metal - L− two-dimensional networks to form entangled 3D frameworks. Furthermore, the photoluminescence and thermal stabilities of complexes 1−6 were investigated. The temperature-dependent magnetic susceptibility measurements of compound 2 show the ferromagnetic interactions between the metal centers mediated through the μ-O and/or O−C−O linkages.
Co-reporter:Qian Chu, Zhi Su, Jian Fan, Taka-aki Okamura, Gao-Chao Lv, Guang-Xiang Liu, Wei-Yin Sun, and Norikazu Ueyama
Crystal Growth & Design 2011 Volume 11(Issue 9) pp:3885-3894
Publication Date(Web):July 12, 2011
DOI:10.1021/cg200416y
Four novel cobalt(II) coordination polymers [Co2(OA)(dib)2(H2O)] (1), [Co2(OA)(bbi)2]·3H2O (2), [Co3(HOA)2(bpe)2(H2O)6]·2H2O (3), and [Co2(OA)(dpe)(H2O)2] (4) were obtained by hydrothermal reactions of Co(NO3)2·6H2O with 3,3′,4,4′-oxidiphthalic acid (H4OA) and corresponding N-donor ligands, namely, 1,4-di(1-imidazolyl)benzene (dib), 1,1′-(1,4-butanediyl)bis(imidazole) (bbi), 1,2-bis(4-pyridyl)ethane (bpe), and 1,2-di(4-pyridyl)ethylene (dpe), respectively. Single crystal X-ray diffraction analysis revealed that 1 is a two-dimensional (2D) network containing infinite -(Co–O–C–O)n- chains, while 2 features a 2D double-layered structure with two types of homochiral helical chains filled in the cavities. Complex 3 is a three-dimensional (3D) framework with (64.82)(66) topology containing infinite 2D networks pillared by bpe bridging ligands. 4 is a (44.66) topological 3D framework with coordinated dpe molecules occupied in the channels. The results revealed that the flexible multi-carboxylate and N-donor auxiliary ligands are effective building blocks in constructing coordination polymers with diverse architectures. In addition, the magnetic properties of 1, 3, and 4 were investigated, and the results showed that weak ferromagnetic interactions occurred between Co(II) ions in 1 and 3, while 4 displays a weak antiferromagnetic behavior.
Co-reporter:Min Chen, Shui-Sheng Chen, Taka-aki Okamura, Zhi Su, Man-Sheng Chen, Yue Zhao, Wei-Yin Sun, and Norikazu Ueyama
Crystal Growth & Design 2011 Volume 11(Issue 5) pp:1901-1912
Publication Date(Web):March 29, 2011
DOI:10.1021/cg200068v
A ligand 5-(4H-1,2,4-triazol-4-yl)benzene-1,3-dicarboxylic acid (H2L) with N- and O-donors was successfully applied to construct a series of coordination complexes [Cu3(μ3-OH)2(HL)4]n (1), [Co(HL)2(H2O)4]·3H2O (2), [Ni(HL)2(H2O)4]·3H2O (3), [Mn(HL)2]n (4), {[Cu2(L)2(μ-OH2)2]·3H2O}n (5), {[Co2(L)2(μ-OH2)2]·3H2O}n (6), {[Ni2(L)2(μ-OH2)2]·3H2O}n (7), and {[Mn(L)(μ-OH2)]·2H2O}n (8) under hydrothermal conditions. By adjusting the reaction pH, H2L ligand is partially deprotonated to give HL– form in 1–4 and completely deprotonated to afford L2– form in 5–8. The structural analyses revealed that complex 1 is a three-dimensional (3D) (3,3,5,6)-connected framework with Point (Schläfli) symbol of (4.6.8)2(42.65.83)2(42.66.86.10)(42.6)2, while 2 and 3 are discrete mononuclear complexes which are extended by hydrogen bonds to form 3D frameworks. The (3,6)-connected 3D framework of 4 is defined as a metal–organic replica of anatase (ant) net with Point (Schläfli) symbol of (42.6)2(44.62.88.10). Complexes 5–7 are isostructural and display (4,5)-connected 3D frameworks with Point (Schläfli) symbol of (42.52.62)(42.53.62.73), and 8 is a binodal (4,6)-connected 3D net with the Point (Schläfli) symbol of (3.54.6)(32.56.66.9). The results revealed that the reaction pH and the metal center play important role in determining the structures of the complexes. Magnetic studies indicate that the mixed μ3-hydroxo and triazolyl bridges in 1 and the double syn–syn carboxylate bridges in 4 mediate antiferromagnetic interactions. The alternating triazolyl and water bridges show alternating ferro- and antiferromagnetic interactions in 5 but antiferromagnetic interactions in 6 and 7. The mixed triazolyl and water bridges show antiferromagnetic interactions in 8.
Co-reporter:Shui-Sheng Chen, Gao-Chao Lv, Jian Fan, Taka-aki Okamura, Min Chen, and Wei-Yin Sun
Crystal Growth & Design 2011 Volume 11(Issue 4) pp:1082-1090
Publication Date(Web):February 25, 2011
DOI:10.1021/cg1012439
Five new entangled metal−organic frameworks {[Co(H2L)2(HCOO)2] (1), [Ni(H2L)2(HCOO)2] (2), [Co(HL)2]·2H2O (3), [Ni(H2L)2(SO4)]·2H2O (4), and [Ag2(L)] (5)} were synthesized by reactions of the corresponding metal salts with rigid ligand 1,4-di(1H-imidazol-4-yl)benzene (H2L). These compounds were characterized by single crystal X-ray structural determination, IR, thermogravimetric analysis, and powder X-ray diffraction. The isostructural behavior is observed between compounds 1 and 2. Both 1 and 2 are 3D frameworks with 3-fold inclined interpenetration of 2D (4,4) networks, where the formate anions generated from the hydrolysis of DMF molecules act as counteranions and terminal ligands. Complex 3 possesses a 6-fold interpenetrated 3D porous dia framework, while 4 is a 4-fold interpenetrated dia net decorated by the sulfate ions, which suppress the occurrence of high-fold interpenetration. In 5 each fully deprotonated ligand (L2−) coordinates with four Ag(I) atoms to form a 3-fold interpenetrated CdSO4-like framework. In addition, the stability and adsorption properties of the complexes were studied.
Co-reporter:Zhi Su, Yue Zhao, Min Chen and Wei-Yin Sun
CrystEngComm 2011 vol. 13(Issue 5) pp:1539-1549
Publication Date(Web):22 Nov 2010
DOI:10.1039/C0CE00527D
Five new coordination polymers [Cd(L)(HPBDA)(H2O)] (1), [Cd2(L)2(PBDA)(H2O)2]·3H2O (2), [Cd2(L)2(PBDA)] (3), [Cd3(L)2(MBDA)2(H2O)2]·2H2O (4) and [Cd2(L)(1,2,3-BTC)(H2O)]·H2O (5) were obtained by reactions of 3,5-di(1H-imidazol-1-yl)benzoic acid (HL) with varied Cd(II) salts in the presence of corresponding auxiliary ligands of 1,4-benzenedicarboxylic acid (H2PBDA), 1,3-benzenedicarboxylic acid (H2MBDA) and 1,2,3-benzenetricarboxylic acid (1,2,3-H3BTC), respectively. Complex 1 with partial deprotonated HPBDA− has one-dimensional (1D) chain structure, while complexes 2 and 3 are interpenetrated three-dimensional (3D) frameworks with InS and dmc topologies, respectively. Complex 4 is a (4,6)-connected 3D framework, and 5 based on tetranuclear Cd(II) secondary building units (SBUs) is a two-dimensional (2D) network. The thermal stability and photoluminescence property of the complexes were investigated.
Co-reporter:Min Chen, Man-Sheng Chen, Taka-aki Okamura, Mei-Fang Lv, Wei-Yin Sun and Norikazu Ueyama
CrystEngComm 2011 vol. 13(Issue 11) pp:3801-3810
Publication Date(Web):04 Apr 2011
DOI:10.1039/C0CE00921K
A series of new 4d–4f heterometallic coordination complexes based on 5-(4H-1,2,4-triazol-4-yl)benzene-1,3-dicarboxylic acid (H2L), namely [AgLn(L)2(H2O)4] [Ln = Nd (1), Eu (2) and Tb (3)], [AgLn(L)2] [Ln = Nd (4), Eu (5) and Tb (6)] and [AgLn(L)2(H2O)]·H2O [Ln = Er (7) and Yb (8)] were successfully synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR, elemental and thermogravimetric analyses. Complexes 1–3 consist of two-dimensional (2D) networks, which are further connected by hydrogen bonding and π–π interactions to give three-dimensional (3D) frameworks. Complexes 4–6 display a 3D (4,6)-connected framework containing 2D heterometallic bilayers. Complexes 7 and 8 are 3-fold interpenetrated (3,4,6)-connected 3D frameworks. The results show that the reaction temperature and the lanthanide have great influence on the structure of the complexes. Luminescent measurements revealed that 2, 3, 5 and 6 exhibit the characteristic emission bands of the lanthanide in the visible region with lifetimes in the range of 0.24–1.81 ms and the strongest emissions are 5D0 → 7F2 for 2 and 5, and 5D4 → 7F5 transitions for 3 and 6.
Co-reporter:Man-Sheng Chen, Min Chen, Taka-aki Okamura, Wei-Yin Sun, Norikazu Ueyama
Microporous and Mesoporous Materials 2011 Volume 139(1–3) pp:25-30
Publication Date(Web):March 2011
DOI:10.1016/j.micromeso.2010.10.011
Two new three-dimensional (3D) coordination polymers [Zn(INAIP)]·2DMF (1) and [Zn(INAIP)]·9H2O (2) have been synthesized by reactions of Zn(NO3)2·6H2O with 5-(isonicotinamido)isophthalic acid (H2INAIP) in N,N-dimethylformamide (DMF) and N,N-diethylformamide (DEF), respectively. The change of solvent leads to the formation of neutral frameworks with different structure, topology as well as different pore size and shape. The X-ray crystallographic structural analysis revealed that complex 1 is an unusual 3D architecture with (3, 6)-connected rutile (rtl) topology containing two-dimensional (2D) (4, 4) networks, while the 3D framework in 2 has (3, 6)-connected (42·6)2(44·62·86·103) topology with 2D kagomé layers. In addition, the stabilities, luminescence and adsorption properties of the complexes were investigated.Graphical abstractResearch highlights► Three-dimensional coordination frameworks with different pore size and shape. ► Solvent effect on formation and structure of metal-organic frameworks. ► Selective sorption behavior of CO2 over N2.
Co-reporter:Man-Sheng Chen, Jian Fan, Taka-aki Okamura, Gao-Chao Lv, Wei-Yin Sun
Inorganica Chimica Acta 2011 Volume 366(Issue 1) pp:268-274
Publication Date(Web):30 January 2011
DOI:10.1016/j.ica.2010.11.019
Three new lanthanide–organic frameworks {[La(IP-py)(HIP-py)(H2O)2]·H2O}n (1), {[Sm2(IP-py)2(IP-pyH)2(H2O)2]·12H2O}n (2) and {[Tb3(IP-py)4(IP-pyH)(H2O)5]·9H2O}n (3) have been prepared by reactions of the corresponding lanthanide salt with 5-(isonicotinamido)isophthalic acid (H2IP-py). The complexes have been fully characterized by means of IR, elemental analyses and single-crystal X-ray diffraction. In compounds 1–3, the lanthanide centers are eight- and nine-coordinated with different coordination geometries and the carboxylate groups of the ligand show different coordination modes leading to the formation of different 2D network structures which are well-defined by the bulky and inert functional groups. Interestingly an unprecedented 2D network of water molecules was observed in complex 2. The luminescent properties of complexes 2 and 3 were investigated.Graphical abstractThree new 2D lanthanide coordination polymers have successfully synthesized via hydrothermal reactions. They have different 2D layer structures, especially, a 2D water net existing in 2. The results show that the 5-(isonicotinamido)isophthalate ligand is versatile and can adopt different coordination modes. The luminescent property of the complexes is investigated.Research highlights► Three new 2D lanthanide coordination polymers with 5-(isonicotinamido)isophthalate. ► 2D networks with different structures. ► Luminescent property of the lanthanide complexes.
Co-reporter:Yue Zhao, Mei-Fang Lv, Jian Fan, Li Luo, Zhi Su, Wei-Yin Sun
Inorganica Chimica Acta 2011 Volume 377(Issue 1) pp:138-143
Publication Date(Web):1 November 2011
DOI:10.1016/j.ica.2011.08.009
Four new coordination complexes [Cd(DPBA-3)2(H2O)2](ClO4)2·2H2O (1), [Cd(DPBA-3)(DMF)(NO3)2]·DMF (2), [Cd3(DPBA-3)2(SCN)6]·2DMF·4H2O (3) and [Zn(DPBA-3)(SCN)2] (4) [DPBA-3 = N,N′-di(pyridin-3-yl)pyridine-3,5-dicarboxamide] have been synthesized and characterized by elemental analysis, IR and single crystal X-ray diffraction. Complexes 1, 3 and 4 exhibit three different types of one-dimensional (1D) chain structures constructed by the metal ions and DPBA-3 ligands, and the Cd(II)-DPBA-3 1D chains in 3 are further linked by bridging SCN− ligands to afford a three-dimensional (3D) framework. Complex 2 possesses a (6,3) two-dimensional (2D) layer structure. In 1–4, the hydrogen bonds involving the amide groups play important role to stabilize the resultant frameworks. The photoluminescence properties of the DPBA-3 and the complexes were studied in the solid state at room temperature.Graphical abstractFour new coordination complexes with N,N′-di(pyridin-3-yl)pyridine-3,5-dicarboxamide have been synthesized and structurally characterized. The complexes show 1D chain, (6,3) 2D network and 3D framework structures. The Luminescence of the complexes was investigated.Highlights► Coordination polymers with N,N′-di(pyridin-3-yl)pyridine-3,5-dicarboxamide. ► Complexes with 1D chain, 2D network and 3D framework structures. ► Luminescence of the complexes.
Co-reporter:Yue Zhao, Li Luo, Chang Liu, Min Chen, Wei-Yin Sun
Inorganic Chemistry Communications 2011 Volume 14(Issue 7) pp:1145-1148
Publication Date(Web):July 2011
DOI:10.1016/j.inoche.2011.04.009
A new coordination polymer [Ag4(dob)4(BF4)4] (1) was synthesized by reaction of rigid ligand 1,3-di(2-oxazolinyl)benzene (dob) with silver(I) tetrafluoroborate and characterized by elemental analysis, single crystal X-ray diffraction and electrospray mass spectrometry. The complex has one-dimensional (1D) helical chain structure which is further linked together by Ag⋯F and hydrogen bonding interactions to form a three-dimensional (3D) supramolecular structure. Complex 1 crystallizes in the noncentrosymmetrical space group and shows second harmonic generation (SHG) and ferroelectric property.A new helical chain coordination polymer [Ag4(dob)4](BF4)4 (1) was synthesized and found to crystallize in the noncentrosymmetrical space group and show second harmonic generation (SHG) and ferroelectric property.Research highlights► Coordination polymer with 1,3-di(2-oxazolinyl)benzene. ► Complex with 1D helical chain structure. ► SHG and ferroelectric property of the complex.
Co-reporter:Zhi Su, Kai Cai, Jian Fan, Shui-Sheng Chen, Man-Sheng Chen and Wei-Yin Sun
CrystEngComm 2010 vol. 12(Issue 1) pp:100-108
Publication Date(Web):15 Sep 2009
DOI:10.1039/B913639H
Four new coordination polymers [Cd(L)(OAc)]·H2O (1), [Cd(L)(µ2-OH)]·H2O (2), [Cd2(L)2(µ3-SO4)(H2O)2]·5H2O (3) and [Cd(L)2]·H2O (4) with different structures and topologies were obtained by solvo/hydrothermal reactions of varied Cd(II) salts with 3,5-di(1H-imidazol-1-yl)benzoic acid (HL) and 1,3-bis(4-pyridyl)propane (bpp). The structures of 1–4 were characterized by single-crystal X-ray diffraction analysis and the results showed that no bpp ligands were incorporated in the resulting complexes, and more interestingly, complexes 1–3 were obtained by reactions of metal to ligand ratio of 1:1, however, when the reactions were carried out with a metal to ligand ratio of 1:2, the resulting complexes had the same structure, namely [Cd(L)2]·H2O (4). In contrast to the 2D network with 63-hcb topology of complex 1 with acetate as terminal ligand, complex 2 is a 3D (4,6)-connected net with µ2-hydroxyl bridging group. Complex 3 is an unprecedented 3D self-penetrating (3,4,5)-connected net with each sulfate as a µ3-bridge to link three Cd(II) atoms, and complex 4 is a 3D self-penetrating (3,5)-connected net formed by two alternate chiral helical chains linking 2-fold interpenetrating 2D (4,82) nets. The results showed that the L− ligand has varied coordination modes and the counteranions have a great impact on the structure of the complexes.
Co-reporter:Man-Sheng Chen, Zheng-Shuai Bai, Taka-aki Okamura, Zhi Su, Shui-Sheng Chen, Wei-Yin Sun and Norikazu Ueyama
CrystEngComm 2010 vol. 12(Issue 6) pp:1935-1944
Publication Date(Web):11 Feb 2010
DOI:10.1039/B921850E
Assembly reactions of pyridyl- and carboxylate-containing ligand 5-(isonicotinamido)isophthalic acid (H2INAIP) with corresponding metal salts result in formation of six new coordination polymers, namely {[Mn(INAIP)(DMF)]·0.5DMF}n (1), {[Mn(INAIP)(H2O)2]·4H2O}n (2), {[Co(INAIP)(H2O)]·2H2O}n (3), {[Co(INAIP)(bpy)0.5]}n (4), {[Co(INAIP)(Him)(H2O)]·H2O}n (5), and {[Cu(INAIP)(Him)(H2O)]·H2O}n (6) (DMF = N,N-dimethylformamide, bpy = 4,4′-bipyridine, Him = imidazole). The results of single-crystal X-ray diffraction analysis indicate that 1 is a two-fold interpenetrated three-dimensional (3D) framework with sra topology, complexes 2, 5 and 6 have two-dimensional (2D) network structure with (6,3) topology, while 3 and 4 have infinite 2D bi-layer structure with different topologies. Complex 3 exhibits a 4-connected network with the Schläfli symbol (43·63), and 4 displays a (4,5)-connected net with Schläfli symbol (43·52·6)(43·55·62). The magnetic and adsorption properties of the complexes were investigated.
Co-reporter:Zhi Su, Man-Sheng Chen, Jian Fan, Min Chen, Shui-Sheng Chen, Li Luo and Wei-Yin Sun
CrystEngComm 2010 vol. 12(Issue 7) pp:2040-2043
Publication Date(Web):05 May 2010
DOI:10.1039/C0CE00054J
Unprecedented two homochiral Cd(II) enantiomers and one achiral Cd(II) complex obtained from one pot reaction with achiral mixed rigid ligands 1,3,5-tris(1-imidazolyl)benzene (tib) and 1,4-benzenedicarboxylate (BDC2−) feature interesting entangled structures in which the ligands display huge distortion, and the homochiral enantiomers show ferroelectric property.
Co-reporter:Shui-Sheng Chen, Zheng-Shuai Bai, Jian Fan, Gao-Chao Lv, Zhi Su, Man-Sheng Chen and Wei-Yin Sun
CrystEngComm 2010 vol. 12(Issue 10) pp:3091-3104
Publication Date(Web):10 Jun 2010
DOI:10.1039/C000373E
Six new metal–organic coordination polymers [Ni(L)(adip)(H2O)] (1), [Co(L)(adip)]·H2O (2), [Cd2(L)(adip)2] (3), [Ni(L)(oxba)]·H2O (4), [Co(L)(obea)]·H2O (5) and [Mn3(L)2(bta)2]·2H2O (6) were synthesized by reactions of the corresponding metal salt with the rigid ligand 1,4-di(1H-imidazol-4-yl)benzene (L) and different multi-carboxylic acids of adipic acid (H2adip), 4,4′-oxybis(benzoic acid) (H2oxba), 1,2-phenylenediacetic acid (H2obea), benzene-1,3,5-triacetic acid (H3bta), respectively. The structures of the complexes were determined by single crystal X-ray diffraction analysis. Complexes 1–4 have entangled structures with different topologies: 1 is a 2-fold interpenetrating two-dimensional (2D) network with (4,4) topology containing rare meso-helical chains; 3 is a three-dimensional (3D) uninodal 8-connected self-penetrating net; 2 and 4 are a 3-fold interpenetrating dmp 3D net. Complex 5 is a 2D network with (4,4) topology, while 6 is a typical (3,8)-connected tfz-d 3D net based on the trinuclear Mn(II) subunits. Complex 3 exhibits intense light blue emission in the solid state at room temperature and the results of magnetic measurements show that there are antiferromagnetic interactions in 6.
Co-reporter:Man-Sheng Chen, Zhi Su, Min Chen, Shui-Sheng Chen, Yi-Zhi Li and Wei-Yin Sun
CrystEngComm 2010 vol. 12(Issue 10) pp:3267-3276
Publication Date(Web):24 Jun 2010
DOI:10.1039/C005207H
Assembly reactions of 5-(isonicotinamido)isophthalic acid (H2INAIP) with Ln2O3 or Ln(NO3)3·6H2O together with NaOH in the presence of AgNO3 result in formation of two series of new 4d–4f heterometallic coordination polymers {[LnAg(INAIP)2]·3H2O}n [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5)] and {[LnAg(INAIP)2(H2O)]·xH2O}n [Ln = La (6), Pr (7), Nd (8), x = 0; Dy (9), Er (10), x = 1]. The results of single-crystal X-ray diffraction analysis indicate that 1–5 are isomorphous and have 2-fold interpenetrated 3D structure with 3-nodal net Point (Schläfli) symbol for net: (4·62)4(44·66·815·103), while 6–10 are isostructural with similar non-interpenetrating 3D frameworks containing 2D lanthanide–carboxylate bilayers. The results indicate that the reaction conditions have great influence on the structure of the resulting complexes in this system. Furthermore, 3 and 5 show intense red and green fluorescent emissions, respectively, and the emission bands of Nd(III) were observed in the near IR region for 1. The magnetic properties of 1–5, 9 and 10 were investigated.
Co-reporter:Zhi Su, You Song, Zheng-Shuai Bai, Jian Fan, Guang-Xiang Liu and Wei-Yin Sun
CrystEngComm 2010 vol. 12(Issue 12) pp:4339-4346
Publication Date(Web):10 Aug 2010
DOI:10.1039/C002366C
Three unprecedented metal-organic frameworks [M3(tib)2(CTC)2]·nH2O [M = Co(II), n = 2 (1); Mn(II), n = 2.92 (2) and Ni(II), n = 2 (3)] based on M3(OCO)6 trinuclear secondary building units (SBUs) have been successfully synthesized by reactions of corresponding metal salt with mixed flexible triacid of 1,3,5-cyclohexanetricarboxylic acid (H3CTC) and rigid imidazol-containing ligand 1,3,5-tris(1-imidazolyl)benzene (tib) under hydrothermal conditions. In 1–3, the CTC3− ligands link the SBUs to form two-dimensional (2D) ‘hxl’ (hexagonal lattice) networks and the tib ligands further pillar the 2D layers leading to the formation of three-dimensional frameworks, which are firstly reported uninodal 10-connected bct nets. The magnetic measurements showed that 1 and 3 exhibit ferromagnetic coupling interactions between the adjacent metal centers with g = 2.63, D = 66.69 cm−1, zJ = 0.68 cm−1 and g = 2.22, J = 6.25 cm−1, zj′ = −0.053 cm−1, respectively, while 2 has antiferromagnetic interaction between the Mn(II) ions with g = 2.01, J = −0.57 cm−1, zj′ = 1.3 × 10−4 cm−1.
Co-reporter:Zhi Su, Jian Fan, Taka-aki Okamura, Man-Sheng Chen, Shui-Sheng Chen, Wei-Yin Sun and Norikazu Ueyama
Crystal Growth & Design 2010 Volume 10(Issue 4) pp:1911-1922
Publication Date(Web):March 18, 2010
DOI:10.1021/cg100020t
Seven new Zn(II) metal−organic frameworks [Zn(tib)2(H2O)](ClO4)2 (1), [Zn4(tib)2(PBDA)3(OH)2]·4H2O (2), [Zn(tib)(HPBDA)]ClO4 (3), [Zn2(tib)(PBDA)Cl2]·2H2O (4), [Zn4(tib)2(PBDA)3Cl2] (5), [Zn2(tib)2(PBDA)](NO3)2·2H2O (6), and [Zn2(tib)(PBDA)I2]·2H2O (7) [tib = 1,3,5-tris(1-imidazolyl)benzene, H2PBDA = p-benzenedicarboxylic acid] have been prepared and characterized by elemental, IR, thermogravimetric and X-ray diffraction analyses. Complexes 1 and 4 are two-dimensional (2D) networks with different topologies, which are further linked together to three-dimensional (3D) frameworks by hydrogen bonds. For 3, partial deprotonated HPBDA− is terminally coordinating to Zn(II) to form a 2D network. Complexes 2, 5, and 7 are 2-fold interpenetrated 3D frameworks, while 6 has a self-penetrating 3D structure. The influences of reaction temperature and counteranion on the structures of the complexes are discussed. The photoluminescence and nonlinear optical properties are investigated.
Co-reporter:Zhi Su, Jian Fan, Taka-aki Okamura, Wei-Yin Sun and Norikazu Ueyama
Crystal Growth & Design 2010 Volume 10(Issue 8) pp:3515
Publication Date(Web):June 18, 2010
DOI:10.1021/cg100418a
Use of unsymmetric ligand 1,2,4-benzenetricarboxylic acid (1,2,4-H3BTC) and controlling the reaction pH value enabled isolation of two novel chiral 3d-3d heterometallic complexes [Zn2Co(tib)3(H2O)5][Zn6(tib)2(1,2,4-BTC)6]·12.7H2O (1) and [ZnCo(tib)(1,2,4-BTC)(H2O)2]Cl·3H2O (2) [tib =1,3,5-tris(1-imidazolyl)benzene]. Comparative study revealed that the use of symmetric ligand 1,3,5-benzenetricarboxylic acid (1,3,5-H3BTC) resulted one achiral 3d-3d heterometallic complex [ZnCo(tib)(1,3,5-BTC)Cl] (3) with 3D structure. Complex 1 is a 2D network with cationic and anionic layers arranged alternately, while 2 is a 3D framework with rare 1D helical water chains. Furthermore, complex 1 displays ferroelectric behavior with a remnant electric polarization (Pr) of ∼0.177 μC/cm2 and an electric coercive field (Ec) of ∼17.68 kV/cm.
Co-reporter:Zhi Su, Shui-Sheng Chen, Jian Fan, Man-Sheng Chen, Yue Zhao and Wei-Yin Sun
Crystal Growth & Design 2010 Volume 10(Issue 8) pp:3675
Publication Date(Web):July 13, 2010
DOI:10.1021/cg100535q
A series of new highly connected MOFs [Cd(L)(PBEA)0.5]·H2O (1), [Cd2(μ3-OH)(L)(PBEA)] (2), [Cd3(μ3-OH)(L)2(PBEA)1.5]·H2O (3), and [Mn(μ2-H2O)(L)(PBEA)0.5] (4) have been synthesized by hydrothermal reactions of 3,5-di(imidazol-1-yl)benzoic acid (HL) and 1,4-benzenediacetic acid (H2PBEA) with different metal salts, and these compounds were fully characterized by X-ray diffraction, IR, elemental analysis, TGA. The photoluminescence of 1−4 and magnetic property of 4 were investigated. Complex 1 is a binodal (3,8)-connected tfz-d net based on the binuclear [Cd2(COO)2] secondary building units (SBU1); while 2 is a binodal (3,10)-connected 3D net based on the tetranuclear motif [Cd4(μ3-OH)2(COO)6] (SBU2). Complex 3 is the first example of trinodal (3,8,10)-connected net based on SBU1 and SBU2, which can be considered as combination of the structural features presented in 1 and 2. Complex 4 is an unprecedented (3,8)-connected net based on the binuclear species [Mn2(μ2-H2O)(COO)2] (SBU3), which showed weak antiferromagnetic interactions between the metal ions. Complexes 1−3 were synthesized under the same experimental conditions except that different Cd(II) salts were used in the syntheses. Notably, although the counteranions of Cd(II) salts are absent from the resulting structures, yet they show subtle influence on the self-assembly process to provide different complexes. The approach of incorporating polynuclear metal cluster into highly connected frameworks and linking the SBUs by organic ligands provides opportunities for the design of new MOFs.
Co-reporter:Qin Hua, Yue Zhao, Guan-Cheng Xu, Man-Sheng Chen, Zhi Su, Kai Cai and Wei-Yin Sun
Crystal Growth & Design 2010 Volume 10(Issue 6) pp:2553
Publication Date(Web):May 10, 2010
DOI:10.1021/cg901480y
Five new coordination polymers, namely, [Cd(L)0.5(HBTC)]·0.2H2O (1), [Cd3(L)2(BTA)2(H2O)2]·H2O (2), [Cd2(L)0.5(BTEC)]·H2O (3), [Zn3(L)(BTC)2(H2O)2]·3H2O (4), and [Zn2(μ2-OH)(L)0.5(BTA)]·H2O (5) were synthesized under hydrothermal conditions by reactions of corresponding Cd(II) or Zn(II) salts with the mixed multidentate ligands of 1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene (L) and 1,3,5-benzenetricarboxylic acid (H3BTC), 1,3,5-benzenetriacetic acid (H3BTA), 1,2,4,5-benzenetetracarboxylic acid (H4BTEC), respectively. The complexes were characterized by single crystal X-ray diffraction, IR, and thermogravimetric and elemental analyses. The Cd(II) complex 1 is a two-dimensional (2D) network with infinite one-dimensional (1D) Cd-HBTC2− chains linked together by L ligands, while the Zn(II) complex 4 with the same mixed ligands has a three-dimensional (3D) structure. The Cd(II) complex with BTA3− and L ligands (2) features an unusual 3D framework, and the Zn(II) complex 5 shows a 3D structure with (63)2(42,84)(4,63,86)2 topology. Complex 3 possesses a 3D structure consisting of a Cd-BTEC4− framework and Cd2O2-L 1D chain. The results showed that the coordination geometry of metal centers and the conformation and coordination mode of organic ligands play an important role in determining the structure and topology of the complexes. The luminescence properties of 1−5 were studied in the solid state at room temperature.
Co-reporter:Shui-Sheng Chen, Jian Fan, Taka-aki Okamura, Man-Sheng Chen, Zhi Su, Wei-Yin Sun and Norikazu Ueyama
Crystal Growth & Design 2010 Volume 10(Issue 2) pp:812
Publication Date(Web):November 24, 2009
DOI:10.1021/cg9011857
Six new coordination polymers [Zn2(L)(OX)2] (1), [Zn2(L)(1,2-BDC)2]·2H2O (2), [Zn2(L)(1,3-BDC)2(H2O)] (3), [Zn(L)(1,4-BDC)] (4), [Zn2(L)(BPDA)2]·2.68H2O (5), and [Zn3(L)2(BTC)2(H2O)2]·3H2O (6) were obtained by hydrothermal reactions of zinc(II) sulfate heptahydrate with rigid ditopic ligand 1,4-di(1H-imidazol-4-yl)benzene (L), sodium hydroxide, or tetrabutylammonium hydroxide and the corresponding carboxylic acid, namely, oxalic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 1,4-benzenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, or 1,3,5-benzenetricarboxylic acid, respectively. The complexes were characterized by single-crystal X-ray diffraction, IR, thermogravimetric, and elemental analyses. Complexes 1 and 2 are three-dimensional (3D) frameworks with infinite two-dimensional (2D) networks pillared by L ligands, and 1 possesses rare self-penetrating mab topology, while 2 shows ins topology. Complex 3 is a 2D bilayer network with infinite one-dimensional double Zn(II)-1,3-BDC2− chains linked by L ligands. Complexes 4−6 have multifold interpenetrating 3D structures: 4 has a 5-fold interpenetrating dia net, 5 has a 4-fold interpenetrating elongated primitive cubic α-Po structure, and 6 has a 3-fold interpenetrating framework. The results showed that the structural diversity of the complexes resulted from the different carboxylate ligands. Solid state properties such as photoluminescence and thermal stability of the complexes have been investigated.
Co-reporter:Zhao-Peng Qi, Kai Cai, Qing Yuan, Taka-aki Okamura, Zheng-Shuai Bai, Wei-Yin Sun, Norikazu Ueyama
Inorganic Chemistry Communications 2010 Volume 13(Issue 7) pp:847-851
Publication Date(Web):July 2010
DOI:10.1016/j.inoche.2010.04.010
A new imidazolate-bridged dicopper complex [Cu2(L)(Im)](ClO4)3·H2O has been synthesized by reaction of new macrocyclic ligand 6, 20-bis(1H-imidazol-4-ylmethyl)-3, 6, 9, 17, 20, 23-hexaazatricyclo[24.3.1.111,15]hentriaconta-1(29), 11, 13, 15(31), 26(30), 27-hexaene (L) with Cu(ClO4)2⋅6H2O and imidazole, and structurally characterized as a model compound of Cu2Zn2-SOD. There is antiferromagnetic interaction with g = 2.08, − 2 J = 66.5 cm− 1 between the two imidazolate-bridged Cu(II) atoms. The complex displays moderate SOD activity with IC50 of 1.42 μM.A new imidazolate-bridged dicopper complex [Cu2(L)(Im)](ClO4)3·H2O [L = 6, 20-bis(1H-imidazol-4-ylmethyl)-3, 6, 9, 17, 20, 23-hexaazatricyclo[24.3.1.111,15]hentriaconta-1(29), 11, 13, 15(31), 26(30), 27-hexaene has been synthesized and structurally characterized as a model compound of Cu2Zn2-SOD.
Co-reporter:Qin Hua, Zhi Su, Yue Zhao, Taka-aki Okamura, Guan-Cheng Xu, Wei-Yin Sun, Norikazu Ueyama
Inorganica Chimica Acta 2010 Volume 363(Issue 13) pp:3550-3557
Publication Date(Web):25 October 2010
DOI:10.1016/j.ica.2010.07.012
Three new coordination complexes [Mn(L)(H2O)2](1,4-BDC)·2H2O (1), [Mn(L)0.5(1,4-BDC)]CH3OH·H2O (2) and [Mn(L)(H2O)2](1,2-HBDC)2·2H2O (3) were synthesized by solvothermal reactions of 1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene (L) and 1,4-benzenedicarboxylic acid (1,4-H2BDC) or 1,2-benzenedicarboxylic acid (1,2-H2BDC) with Mn(II) salt, and characterized by single crystal X-ray diffraction, IR, thermogravimetric and elemental analyses. In complexes 1 and 3, each ligand L links four Mn(II) atoms to form two-dimensional (2D) cationic network with non-coordinated 1,4-BDC2− and 1,2-HBDC− anions lying in the voids between the two adjacent layers, respectively. The 2D layers are further connected together by hydrogen bonds to give three-dimensional (3D) supramolecular structures. However, the 1,4-BDC2− in 2 acts not only as counteranion, but also as bridging ligand leading to the formation of 2-fold interpenetrated 3D framework with pcu (primitive cubic unit) topology. The Mn(II) atoms bridged by carboxylate groups in 2 show antiferromagnetic interactions.Solvothermal reactions of Mn(II) salt with tetradentate imidazole-containing ligand in the presence of different benzenedicarboxylic acid were carried out and complexes with different structure were obtained. The effect of the metal-to-ligand ratio was discussed. The magnetic property of complex 2 was explored.
Co-reporter:Zhi Su, Zhi-Bin Wang, Wei-Yin Sun
Inorganic Chemistry Communications 2010 Volume 13(Issue 11) pp:1278-1280
Publication Date(Web):November 2010
DOI:10.1016/j.inoche.2010.07.015
Two novel coordination polymers [Zn2(tib)(chda)Cl2] (1) and [Zn(tib)I]I (2) have been prepared by reactions of 1,3,5-tris(1-imidazolyl)benzene (tib) and 1,2-cyclohexanedicarboxylic acid (H2chda) with corresponding Zn(II) salts, respectively. Complex 1 has a three-dimensional (3D) structure with rare gra (graphite) topology, while 2 is a typical two-dimensional (2D) (4·82) network. The results revealed that the counteranion plays a subtle and important role in the assembly procedure. Photoluminescent property of the complexes was investigated.Two novel coordination polymers [Zn2(tib)(chda)Cl2] (1) and [Zn(tib)I]I (2) [tib = 1,3,5-tris(1-imidazolyl)benzene, H2chda = 1,2-cyclohexanedicarboxylic acid] with rare gra (graphite) topological 3D framework and 2D (4·82) network have been synthesized and structurally characterized, respectively.
Co-reporter:Jing Xu, Qing Liu, Wei-Yin Sun
Solid State Sciences 2010 Volume 12(Issue 9) pp:1575-1579
Publication Date(Web):September 2010
DOI:10.1016/j.solidstatesciences.2010.07.002
Hydrothermal synthetic method has been used to prepare complex [ZnL]n (1) (H2L = 4-[(1H-imidazol-4-yl)methylamino]benzoic acid) as spherical microparticles. Slow morphological changes from small spindle-shaped particles to smoother spherical particles in the growth process of complex 1 were observed. Subsequently complex 1 was used as precursor as well as sacrificial template to synthesize hexagonal ZnO nanomaterials by calcination in air. The structure of the final products and the formation process were characterized by measurements of X-ray powder diffraction (XRPD), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The formation mechanism of the final nanorods was proposed on the basis of the structural change of complex 1 in the calcination process. The photocatalytic properties of complex 1 and prepared ZnO have also been studied, and the results showed that all these nano-/micromaterials have photocatalytic properties and ZnO formed under lower calcinated temperature has higher photocatalytic activity.
Co-reporter:Gang Wu, Xiao-Feng Wang, Taka-aki Okamura, Min Chen, Wei-Yin Sun, Norikazu Ueyama
Journal of Solid State Chemistry 2010 Volume 183(Issue 9) pp:2174-2182
Publication Date(Web):September 2010
DOI:10.1016/j.jssc.2010.07.036
Five new silver(I) complexes [Ag2(L2)2](BF4)2·CH3CN·CH3OH (1), [Ag(L2)(CF3SO3)] (2), [Ag(L3)]ClO4·CH3OH (3), [Ag2(L3)2](CF3SO3)2·CH3CN·CH3OH·H2O (4) and [Ag(L3)]PF6·2CH3CN (5) [L2=1,3,5-tris(2-pyridylmethoxyl)benzene, L3=1,3,5-tris(3-pyridylmethoxyl)benzene] were synthesized and characterized by single crystal X-ray diffraction analyses. In complexes 1–5, ligands L2 and L3 show different conformations and act as three-connectors, while the Ag(I) atom serves as three-connecting node to result in the formation of 2D and 3D frameworks. Complexes 1 and 2 with different counteranions have similar 2D network structure with the same (4,82) topology. Complex 3 has a 3D structure with (10,3)-a topology while complexes 4 and 5 have the same 2D (6,3) topological structure. The results showed that the structure of organic ligands and counteranions play subtle but important role in determining the structure of the complexes. In addition, the photoluminescence and anion-exchange properties of the complexes were investigated in the solid state at room temperature.Graphical abstractFive new silver(I) coordination frameworks with different topology were obtained and their structures were determined by single crystal X-ray diffraction studies. The influence of counteranion and ligand on the structure of complexes was discussed, the photoluminescence and anion-exchange properties were reported.
Co-reporter:Zhao-Peng Qi, Qing Yuan, Shu-An Li, Taka-aki Okamura, Kai Cai, Wei-Yin Sun, Norikazu Ueyama
Journal of Molecular Structure 2010 Volume 973(1–3) pp:104-115
Publication Date(Web):2 June 2010
DOI:10.1016/j.molstruc.2010.03.048
Seven new metal complexes [Zn2(L)Br2](ClO4)2 (1), [Cu2(L)Br2]Br2·2H2O (2), [Cu2(L)(H2O)2](ClO4)4·1.03H2O (3), [Cu6(L)3(H2O)2Br2(N3)](ClO4)9·2H2O (4), [Cu4(L)2Br4(im)2]Br2·15H2O (5), [Cu2(L)(bpy)2](ClO4)4·2bpy·2H2O (6) and [Cu2(L)(tp)]Br2·6H2O (7) (N3- = azide anion; im− = imdazolate anion; bpy = 4,4′-bipyridine; tp2− = terephthalate dianion) have been synthesized by reactions of macrocyclic ligand 3,6,9,12,20,23,26,29-octaazatricyclo[29.3.1.114,18]hexatriaconta-1(34),14,16,18(36),31(35),32-hexaene (L) and metal salts with different counteranion and/or co-ligand. Interestingly, there are [Zn2L]4+/[Cu2L]4+ dinuclear units with different conformations of chair-type in 1, 2, 6 and 7, boat-type in 5 and mixed chair- and boat-types in 3, 4. The complexes 1, 2, 3 and 6 have dinuclear molecular structure, and 4 has dimer of [Cu2L]4+ linked by azide and 5 displays tetranuclear molecular rectangle bridged by imidazolate groups, while 7 has 1D chain structure in which the [Cu2L]4+ units linked by terephthalate anions. The results revealed that the structure, coordination ability and coordination mode of anions and/or co-ligands have great impact on the structure of the complexes.
Co-reporter:Zhi Su;Jian Fan;WeiYin Sun
Science China Chemistry 2010 Volume 53( Issue 10) pp:2164-2169
Publication Date(Web):2010 October
DOI:10.1007/s11426-010-4112-y
Three novel coordination polymers, [Ni2(tib)2(btec)]·2H2O (1), [Co2(tib)2(btec)]·2H2O (2) and [Zn4(tib)2(btec)Cl4]·2H2O (3), have been synthesized by using mixed ligands of 1,3,5-tris(1-imidazolyl)benzene (tib) and 1,2,4,5-benzenetetracarboxylic acid (H4btec) under hydrothermal conditions. Complexes 1 and 2 have the same structure and are rare three-dimensional (3D) self-penetrating (3,4,5)-connected nets, while complex 3 is an unprecedented (3,4)-connected 3D net. The different structures of 1 (2) and 3 are ascribed to the distinct coordination geometry of the metal centers. The thermal stability and photoluminescence property of the complexes were investigated.
Co-reporter:Man-Sheng Chen, Qin Hua, Zheng-Shuai Bai, Taka-aki Okamura, Zhi Su, Wei-Yin Sun, Norikazu Ueyama
Polyhedron 2010 29(12) pp: 2454-2461
Publication Date(Web):
DOI:10.1016/j.poly.2010.05.014
Co-reporter:Zhi Su, Jing Xu, Jian Fan, De-Jun Liu, Qian Chu, Man-Sheng Chen, Shui-Sheng Chen, Guang-Xiang Liu, Xiao-Feng Wang and Wei-Yin Sun
Crystal Growth & Design 2009 Volume 9(Issue 6) pp:2801
Publication Date(Web):April 22, 2009
DOI:10.1021/cg900059m
This work presents systematic investigation on reactions of zinc(II) salts with a rigid tripodal ligand in the presence of different benzenedicarboxylic acids. Seven new coordination polymers [Zn(tib)(1,3-BDC)]·H2O (1), [Zn2(tib)(1,3-BDC)2(H2O)]·2H2O (2), [Zn2(tib)(1,2-BDC)Cl2] (3), [Zn4(tib)2(1,2-BDC)4]·2H2O (4), [Zn2(tib)2(1,2-BDC)](NO3)2 (5), [Zn2(tib)2(1,2-BDC)]I2 (6), and [Zn3(tib)2(4-BPA)Cl4]·2H2O (7) [tib = 1,3,5-tris(1-imidazolyl)benzene, 1,3-BDC2− = 1,3-benzenedicarboxylate, 1,2-BDC2− = 1,2-benzenedicarboxylate, 4-BPA2− = 4-bromo-1,2-benzenedicarboxylate] were obtained, and they were characterized by single crystal X-ray diffraction, IR, thermogravimetric and elemental analyses. Complexes 1, 4, and 7 are two-dimensional (2D) networks containing infinite one-dimensional (1D) Zn(II)-tib chains linked together by auxiliary dicarboxylate ligands. Complexes 2 with 2-fold interpenetration and 3 are three-dimensional (3D) frameworks containing infinite 2D networks pillared by 1,2-BDC2− ligands, while 5 and 6 feature unusual 3D supramolecular architectures with 4.82 networks linked by 1,2-BDC2− ligands. The results showed that the dicarboxylate auxiliary ligands and the counteranions have a great influence on the structure of the complexes. The luminescence properties of 1−7 in the solid state were studied.
Co-reporter:Zhi Su, Zheng-Shuai Bai, Jian Fan, Jing Xu and Wei-Yin Sun
Crystal Growth & Design 2009 Volume 9(Issue 12) pp:5190-5196
Publication Date(Web):November 12, 2009
DOI:10.1021/cg900613p
Two new 3d-3d homo- and heterometallic coordination polymers with mixed organic ligands, namely, [Zn2(IBC)(BTC)(H2O)]·H2O (1) and [CdCo(IBC)(BTC)(H2O)] (2) [HIBC = 3,5-di(1H-imidazol-1-yl)benzoic acid, H3BTC = 1,3,5-benzenetricarboxylic acid], have been synthesized and fully characterized by X-ray diffraction, IR, elemental analysis, thermogravimetric analysis, photoluminescence, and magnetic measurements. Complex 1 with homonuclear Zn(II) is a rare three-dimensional (3D) (3,6)-connected rtl (rutile) framework with [Zn2O2] and [Zn2(OCO)2] two different kinds of binuclear Zn(II) secondary building units (SBUs). While complex 2 with heteronuclear Cd(II) and Co(II) atoms is a 3D framework based on [Cd2O2] and [Co2O2] SBUs. In 2, the SBUs are extended into an infinite eight-connected rare hex-type (hexagonal-type) network. The binuclear [Co2O2] SBU in 2 shows antiferromagnetic interactions. Both 1 and 2 were constructed by the same ligands, however with completely different structures and topologies, the results revealed that the coordination geometries of the metal centers have a subtle influence on the structure of the complexes.
Co-reporter:Guan-Cheng Xu, Yu-Jie Ding, Taka-aki Okamura, Yong-Qing Huang, Zheng-Shuai Bai, Qing Hua, Guang-Xiang Liu, Wei-Yin Sun and Norikazu Ueyama
Crystal Growth & Design 2009 Volume 9(Issue 1) pp:395-403
Publication Date(Web):November 19, 2008
DOI:10.1021/cg800600g
Seven new coordination polymers {[Cu3(tib)4](NO3)6·4.94H2O}n (1), {[Cu2(tib)2(SO4)2]·2EtOH·2H2O}n (2), [Cu(tib)Cl2]n (3), {[Cd(tib)2](NO3)2·4H2O}n (4), {[Cd(tib)(H2O)2(SO4)]·EtOH·H2O}n (5) {[Co(tib)(H2O)2(SO4)]·EtOH·H2O}n (6), and {[Ni(tib)(H2O)2(SO4)]·EtOH·H2O}n (7) (EtOH = ethanol) were prepared by reactions of flexible tripodal ligand 1,3,5-tris(imidazol-1-ylmethyl)benzene (tib) with the corresponding metal salts. Their structures were determined by X-ray crystallography. The different structures of 1−3 as well as 4 and 5 indicate that the counteranions play an important role in the construction of coordination polymers. The distinct structures of Cu(II) and Cd(II) complexes with the same counteranion demonstrate that the metal centers with different coordination geometry have a significant influence on the structures. The same 1D chain structure of 5−7 indicated that the metal centers with the same octahedral coordination geometry do not affect the structure of the complexes. On the other hand, ligand tib acts as a three-connecting linker to connect three M(II) centers with different conformations. In 1, two different conformations (cis, trans, trans-, and trans-) of tib coexist. In 2−4, tib adopts the cis, trans, trans-conformation, while in the case of 5−7, tib has the cis, cis, cis-conformation. The results attest that the flexible tripodal ligand tib can adopt different conformations to form complexes with varied structures. Furthermore, the reversible anion exchange properties of 1 and 4 were studied.
Co-reporter:Zheng-Shuai Bai, Jing Xu, Taka-aki Okamura, Man-Sheng Chen, Wei-Yin Sun and Norikazu Ueyama
Dalton Transactions 2009 (Issue 14) pp:2528-2539
Publication Date(Web):12 Feb 2009
DOI:10.1039/B816205K
Six novel three-dimensional (3D) dense organic–lanthanide(III) frameworks with formula {[Ln(HBPTCA)(H2O)]·3H2O}n [Ln = La (1), Ce (2), Sm (3)] and [Ln4(BPTCA)3(H2O)4]n [Ln = Tb (4), Dy (5), Ho (6)] were obtained by reactions of the corresponding lanthanide nitrate salt with 4,4′-bipyridine-2,2′,6,6′-tetracarboxylic acid (H4BPTCA) under different conditions. Complexes 1–3 have the same structure with (4, 62)2(42, 610, 83) topology, which is rare binodal (3, 6)-connecting rutile structure, while the complexes 4–6 also with the same structure have different topology of (42, 6)4(6, 82)4(43, 63)4(42, 64)6(44, 65, 85, 10). The results indicate that the reaction conditions have great influence on the structure of the resulted complexes in this system. In addition, the H4BPTCA was found to be an effective bridging ligand for construction of novel lanthanide-based dense hybrids, and two new coordination modes of the BPTCA4− were found in the complexes. The photoluminescent property of 4 and magnetic properties of 2, 5 and 6 were also investigated.
Co-reporter:Guan-Cheng Xu, Qin Hua, Taka-aki Okamura, Zheng-Shuai Bai, Yu-Jie Ding, Yong-Qing Huang, Guang-Xiang Liu, Wei-Yin Sun and Norikazu Ueyama
CrystEngComm 2009 vol. 11(Issue 2) pp:261-270
Publication Date(Web):06 Nov 2008
DOI:10.1039/B813220H
Six new three-dimensional (3D) Cd(II) coordination polymers, {[Cd2(L)3](NO3)4·6H2O}n (1), {[Cd2(L)3](ClO4)4·2H2O}n (2), {[Cd2(L)3](BF4)4·2H2O}n (3), {[Cd(L)Cl2]·2H2O}n (4), {[Cd2(L)2(SO4)2(H2O)]·2H2O}n (5) and {[Cd2(L)(SO4)2(H2O)3]·4H2O}n (6), have been solvothermally synthesized by reactions of the corresponding Cd(II) salts with flexible tetradentate ligand 1,2,4,5-tetrakis(imidazol-1-ylmethyl)benzene (L), respectively. The X-ray diffraction analysis revealed that the isostructural 1, 2 and 3 have 3D framework structures with (46·66·83)2(42·63·8)3 topology. Complex 4 has a different 3D framework structure with (65·8) topology, while 5 and 6 possess pillared-layer and plywood-like 3D framework structures, respectively. The distinct structures of 1 (2, 3), 4 and 5 indicate that the counter anions with different coordination abilities play an important role in the formation of coordination polymers. Complexes 5 and 6, synthesized by the same reactants in the same solvent, have different structures due to the different metal/ligand ratio. In addition, the results also demonstrated that the flexible tetradentate ligand L can adopt varied conformations and coordination modes to form complexes with different structures. L adopts up,up,down,down-conformation in 1–3, while in 4, it has a up,down-conformation. It is interesting that two different conformations of up,down,down,up- and H-type of L coexist in 5. In the case of 6, L has H-type conformation. Furthermore, the reversible anion exchange property of 1 was studied.
Co-reporter:Zhi Su, Zheng-Shuai Bai, Jing Xu, Taka-aki Okamura, Guang-Xiang Liu, Qian Chu, Xiao-Feng Wang, Wei-Yin Sun and Norikazu Ueyama
CrystEngComm 2009 vol. 11(Issue 5) pp:873-880
Publication Date(Web):02 Feb 2009
DOI:10.1039/B822394G
Two novel cobalt(II) complexes [Co(L)(NO3)] (1) and [Co(L)(H2O)2]ClO4 (2) were synthesized by reactions of 3,5-di(1H-imidazol-1-yl)benzoic acid (HL) with corresponding cobalt(II) salts, and their structures were determined by single crystal X-ray diffraction analysis. In the title complexes, the carboxylate group of L− ligand adopts a µ2–ŋ1:ŋ1-bridging mode to connect two cobalt(II) atoms, and each L− ligand acts as a 4-connector, and the cobalt(II) has distorted octahedral coordination geometry. In 1, one oxygen atom of the nitrate anion links two cobalt(II) atoms to complete a 3D structure which is a binodal (4,6)-connected net with Schläfli symbol of (3·42·52·6)(32·42·52·64·74·8). While in 2, the 3D structure has topology related to SrAl2, CeCu2 and KHg2 with Schläfli symbol of (42·63·8) and there are 1D channels filled with perchlorate anions. The results revealed that the nature of the counteranions, such as their shape, size and coordination ability, has a remarkable influence on the structure of the complexes. The results of the magnetic measurements showed that there are antiferromagnetic interactions between the neighboring Co(II). Furthermore, complex 2 exhibited a modest second-harmonic-generation (SHG) efficiency and anion-exchange property.
Co-reporter:Qing Yuan, Kai Cai, Zhao-Peng Qi, Zhen-Shuai Bai, Zhi Su, Wei-Yin Sun
Journal of Inorganic Biochemistry 2009 Volume 103(Issue 8) pp:1156-1161
Publication Date(Web):August 2009
DOI:10.1016/j.jinorgbio.2009.06.003
Two new homo- and hetero-dinuclear complexes, [Cu2L(im)](ClO4)3⋅4H2O (1) and [CuZnL(im)](ClO4)3⋅4H2O (2) (where Im=1H-1midazole and L = 3, 6, 9, 16, 19, 22-hexaaza-6, 19-bis(1H-imidazol-4-ylmethyl)tricycle[22, 2, 2, 211,14]triaconta-1, 11, 13, 24, 27, 29-hexaene) were synthesized and characterized as model compounds for the active site of copper(II)–zinc(II) superoxide dismutase (Cu2Zn2–SOD). X-ray crystal structure analysis revealed that the metal centers in both complexes exhibit distorted trigonal-bipyramid coordination geometry and the Cu⋯Cu and Cu⋯Zn distances are both 6.02 Å. Magnetic and ESR spectral measurements of 1 showed antiferromagnetic exchange interactions between the imidazolate-bridged Cu(II) ions. The ESR spectrum of 2 displays typical signals of mononuclear Cu(II) complex, demonstrating the formation of heterodinuclear complex 2 rather than a mixture of homodinuclear Cu(II)/Zn(II) complexes. pH-dependent ESR and UV–visible spectral measurements manifest that the imidazolate exists as a bridging ligand from pH 6 to 11 for both complexes. The IC50 values of 1.96 and 1.57 μM [per Cu(II) ion] for 1 and 2 suggest that they are good models for the Cu2Zn2–SOD.
Co-reporter:Jing Xu, Qing Liu, Taka-aki Okamura, Man-Sheng Chen, Wei-Yin Sun, Norikazu Ueyama
Solid State Sciences 2009 Volume 11(Issue 11) pp:1903-1907
Publication Date(Web):November 2009
DOI:10.1016/j.solidstatesciences.2009.07.016
Reactions of ligand 5-(1H-imidazol-4-yl)methylaminoisophthalic acid (H3L) with varied lanthanide metal salts led to the formation of five scalelike 2D layered complexes {[Ln(H2L)(HL)(H2O)2]·H2O}n [Ln(III) = Pr(III) (1), Nd(III) (2), Sm(III) (3), Gd(III) (4), Tb(III) (5)]. The single crystal X-ray diffraction analyses revealed that five complexes crystallized in the same monoclinic space group C2/c are isomorphous and isostructural, and the 2D networks are further connected by hydrogen bonds and π–π interactions resulting in formation of 3D structures. Investigations on the visible luminescent property of the complexes demonstrate that compounds 3 and 5 show characteristic emissions of Sm(III) and Tb(III) in the solid state at room temperature, respectively.
Co-reporter:Man-Sheng Chen, Zheng-Shuai Bai, Zhi Su, Shui-Sheng Chen, Wei-Yin Sun
Inorganic Chemistry Communications 2009 Volume 12(Issue 6) pp:530-533
Publication Date(Web):June 2009
DOI:10.1016/j.inoche.2009.04.015
A new three-dimensional nickel(II) metal-organic framework [Ni(INAIP)(H2O)2]n · nH2O (1) [H2INAIP = 5-(isonicotinamido)isophthalic acid] was synthesized under hydrothermal conditions, and characterized by single-crystal X-ray structure determination, thermogravimetric analysis, X-ray powder diffraction, IR and magnetic studies. The compound 1 has (10, 3)-b topology with not well known fourfold interpenetration, in which both Ni(II) atoms and INAIP2− ligands act as three-connected nodes.A novel 3D Ni(II) coordination polymer, [Ni(INAIP)(H2O)2]n · nH2O (1) [H2INAIP = 5-(isonicotinamido)isophthalic acid], has been hydrothermal synthesized and characterized. Complex 1 shows a rare fourfold interpenetrated (10, 3)-b net.
Co-reporter:Jing Xu, Qing Yuan, Zheng-Shuai Bai, Zhi Su, Wei-Yin Sun
Inorganic Chemistry Communications 2009 Volume 12(Issue 1) pp:58-61
Publication Date(Web):January 2009
DOI:10.1016/j.inoche.2008.11.006
Complete and partial deprotonation of new ligand 4-[(1H-imidazol-4-yl)methylamino]benzoic acid (H2L) under hydrothermal conditions lead to the formation of two novel coordination polymers [ZnL]n (1) and [Ag(HL)]n (2). Complex 1 displays a rare three-dimensional (3,6)-connected rtl framework with (4 · 62)2(42 · 610 · 83) topology, while 2 has a one-dimensional chair-like structure including significant argentophilic Ag–Ag interactions. Both 1 and 2 show remarkable thermal stability and complex 1 was found to show strong blue luminescence with emission maxima at 381 nm upon excitation at 347 nm in the solid state at room temperature.Two novel complexes, [ZnL]n (1) and [Ag(HL)]n (2) (H2L = 4-[(1H-imidazol-4-yl)methylamino]benzoic acid) were synthesized under hydrothermal conditions. Complex 1 displays a rare three-dimensional (3,6)-connected rtl framework, while 2 has a one-dimensional chair-like structure including significant argentophilic Ag–Ag interactions.
Co-reporter:Xia-Ying Zhou, Yong-Qing Huang, Wei-Yin Sun
Inorganica Chimica Acta 2009 Volume 362(Issue 5) pp:1399-1404
Publication Date(Web):1 April 2009
DOI:10.1016/j.ica.2008.06.013
Reactions of ligand 2-(1H-1,2,4-triazol-1-yl)acetic acid (HL) with varied metal salts of Cu(II), Co(II), Ni(II), Zn(II), Cd(II) and Ag(I) result in formation of six new coordination complexes, {[Cu(L)2] · 3H2O}n (1), [Co(L)2(H2O)2]n (2), [Ni(L)2(H2O)2]n (3), [Zn(L)2(H2O)2]n, (4), [Cd(L)2]n (5) and [Ag(L)]n (6), and their structures were determined by X-ray crystallography. Complexes 1, 2, 3 and 4 with square-planar or octahedral metal centers have similar two-dimensional (2D) network structure with (4, 4) topology, while complex 5 displays a 2D structure with (6, 3)-connected topology. Complex 6 has a three-dimensional (3D) structure, in which the Ag(I) has tetrahedral coordination geometry. Ligand L− acts as a 2-connected rod (bridging ligand) in 1, 2, 3 and 4, and acts as 3-connected nodes in 5 and 6. The results indicate that the coordination modes of the ligand and metal centers have great influence on the structures of the complexes. In addition, the photoluminescent properties of ligand HL and complexes 4 and 5 were studied in the solid state at room temperature.Reactions of ligand 2-(1H-1,2,4-triazol-1-yl)acetic acid (HL) with varied metal salts result in formation of six new coordination complexes with 3D and 2D network structures with (4, 4) and (6, 3)-connected topologies. The results indicate that the coordination modes of the ligand and metal centers have great influence on the structures of the complexes.
Co-reporter:Jing Xu, Zhi Su, Man-Sheng Chen, Shui-Sheng Chen, Wei-Yin Sun
Inorganica Chimica Acta 2009 Volume 362(Issue 11) pp:4002-4008
Publication Date(Web):15 August 2009
DOI:10.1016/j.ica.2009.05.048
Three new coordination polymers {[Cu(HL)(H2O)]·H2O}n (1), [Ag(H2L)]n (2), and {[Co(HL)(phen)(H2O)]·8H2O}n (3) [H3L = 5-(1H-imidazol-4-ylmethyl)aminoisophthalic acid, phen = 1,10-phenanthroline] have been synthesized under hydrothermal conditions. The results of X-ray diffraction analysis revealed that complex 1 displays (3, 3)-connected 2D network with (4, 82) topology, while complexes 2 and 3 have infinite 1D chain structure, in which one of the two carboxylic groups of H2L−/HL2− is uncoordinated. The 2D layers of 1 or the 1D chains of 2 and 3 are further linked together by hydrogen bonds and π–π interactions to form 3D supramolecular frameworks. Moreover, the electrochemical properties of complexes 1 and 2 have been studied by modified glassy carbon electrodes of 1 (Cu-GCE) and 2 (Ag-GCE), and the results indicate that the Cu-GCE and Ag-GCE show one-electron redox peaks. In addition, both Cu-GCE and Ag-GCE have good electrocatalytic activities toward the reduction of H2O2 in phosphate buffer (pH 5.5) solution.Three new coordination polymers {[Cu(HL)(H2O)]·H2O}n (1), [Ag(H2L)]n (2), and {[Co(HL)(phen)(H2O)]·8H2O}n (3) [H3L = 5-(1H-imidazol-4-ylmethyl)aminoisophthalic acid, phen = 1,10-phenanthroline] with 1D chain and 2D network structures have been synthesized, and their electrochemical property and electrocatalytic activity toward the reduction of hydrogen peroxide were studied.
Co-reporter:Jing XU;Zhengshuai BAI ;Weiyin SUN
Chinese Journal of Chemistry 2009 Volume 27( Issue 3) pp:501-504
Publication Date(Web):
DOI:10.1002/cjoc.200990082
Abstract
A new supramolecular framework [Co(µ2-ClO4)2(H2O)2]·2MA (1) [MA=melamine (C3H6N6)] has been synthesized by a hydrothermal method. Interestingly, there are inorganic and organic building blocks with two different supramolecular synthons: (a) 2D (4,4) network constructed by infinite inorganic 1D chains through interchain hydrogen bonding interactions; (b) 1D zigzag organic chains formed by hydrogen bonds, which further stack up through π-π interactions between the two adjacent MA molecules. The entire structure of 1 is a 3D supramolecular framework resulting from the presence of abundant hydrogen bonds between infinite [Co(µ2-ClO4)2(H2O)2]n chains and zigzag MA chains in different sheets. 1 gives a nice example of supramolecular framework based on non-covalent interactions including hydrogen bonding and π-π interactions.
Co-reporter:Zhi Su, Jing Xu, Yong-Qing Huang, Taka-aki Okamura, Guang-Xiang Liu, Zheng-Shuai Bai, Man-Sheng Chen, Shui-Sheng Chen, Wei-Yin Sun
Journal of Solid State Chemistry 2009 Volume 182(Issue 6) pp:1417-1423
Publication Date(Web):June 2009
DOI:10.1016/j.jssc.2009.03.010
Hydrothermal reactions of cadmium(II) or silver(I) salt, NaN3, 4-(imidazol-1-ylmethyl)benzonitrile (IBN) yield three coordination complexes, [Cd(L)2(H2O)2]·3H2O (1), [Cd3(L)5(OH)] (2) and [Ag2(L)2] (3) where HL=1-(5-tetrazolyl)-4-(imidazol-1-ylmethyl)benzene. The crystal structure analysis revealed that 1 has 1D hinged-chain structure containing 24-membered ring with a Cd···Cd intra-chain distance of 13.18 Å, while 2 is 1D ladder-like chain with Cd3O core. However, the complex 3 is a 3D 4-connected framework with Schläfli symbol of (42·63·8)(43·62·8). The L− ligand was found to show four different coordination modes in 1–3, as 2-, 3- and 4-connector, respectively. The results indicate that the coordination modes of the ligand and metal centers with different coordination geometry have great influence on the structures of the complexes. In addition, the photoluminescence of the complexes were studied in the solid state at room temperature.Three novel coordination polymers were obtained with in situ ligand formation through Sharpless's [3+2] reaction. The structure and luminescence properties of the complexes were investigated.
Co-reporter:ZhengShuai Bai;ShuiSheng Chen;ZhengHua Zhang
Science China Chemistry 2009 Volume 52( Issue 4) pp:459-464
Publication Date(Web):2009 April
DOI:10.1007/s11426-009-0044-9
Two novel interpenetrated coordination polymers, [Zn(IBA)2]n (1) and {[Cd(IBA)2(H2O)]·4H2O}n (2), have been synthesized by using 4-imidazole-benzoic acid (HIBA) as ligand under hydrothermal conditions. Complex 1 crystallizes in a chiral space group and has a two-fold interpenetrated 2D network structure with (4,4) topology, while complex 2 is a 3D porous dia network with four nets interpenetrating each other. The SHG activity of 1 and the photoluminescent property of 2 have been investigated.
Co-reporter:Jing Xu, Zheng-Shuai Bai, Taka-aki Okamura, Man-Sheng Chen, Wei-Yin Sun, Norikazu Ueyama
Polyhedron 2009 28(12) pp: 2480-2486
Publication Date(Web):
DOI:10.1016/j.poly.2009.04.032
Co-reporter:Zheng-Shuai Bai, Zhao-Peng Qi, Yi Lu, Qing Yuan and Wei-Yin Sun
Crystal Growth & Design 2008 Volume 8(Issue 6) pp:1924
Publication Date(Web):May 13, 2008
DOI:10.1021/cg7011952
Three new inorganic–organic hybrid frameworks, [Mn 2(BPTCA)(phen) 2·H 2O] n ( 1), [Mn 4(BPTCA) 2(H 2O) 10·2.5H 2O] n ( 2), and [Mn 2(BPTCA)(μ 2-H 2O) 2] n ( 3) (BPTCA 4− = 4,4′-bipyridine-2,2′,6,6′-tetracarboxylate; phen = 1,10-phenanthroline), have been synthesized under hydrothermal conditions. Complex 1 is a two-dimensional (2D) network constructed by infinite O−Mn−O−C−O−Mn- chains and BPTCA 4− ligands, and an intriguing slide fastener-like three-dimensional (3D) framework structure is formed by the π···π interactions between the phen molecules. Complex 2 crystallized in a chiral space group P2 1 has a 2D network structure formed by Mn 4 cluster units and BPTCA 4− linkers, while complex 3 obtained at higher temperature than 2 is a 3D porous architecture. The result implies that the hydrothermal reaction temperature has a great influence on the structure of the complexes in this system. The magnetic behaviors of the complexes have been investigated and 2 showed modest powder second harmonic generation activity.
Co-reporter:Yan Wang, Taka-aki Okamura, Wei-Yin Sun and Norikazu Ueyama
Crystal Growth & Design 2008 Volume 8(Issue 3) pp:802
Publication Date(Web):February 8, 2008
DOI:10.1021/cg701242z
N′,N″,N′′′-Tris(pyrid-4-ylmethyl)-1,3,5-benzenetricarboxamide (TPMBA-4) reacts with Cu(BF4)2·6H2O to form a zero-dimensional cagelike complex [CuII6(OH)6(TPMBA-4)8](BF4)3(OH)3·85H2O (1). Interestingly, X-ray crystallographic analysis revealed that large (H2O)76(OH)6 clusters with outer-shell (H2O)56(OH)6 and inner-hosted (H2O)20 ones are encapsulated in the cavity of 1. It presents a new mode of association of water molecules for research on water or ice.
Co-reporter:Yong-Qing Huang, Zhong-Liang Shen, Taka-aki Okamura, Yan Wang, Xiao-Feng Wang, Wei-Yin Sun, Jin-Quan Yu and Norikazu Ueyama
Dalton Transactions 2008 (Issue 2) pp:204-213
Publication Date(Web):04 Dec 2007
DOI:10.1039/B714502K
Seven new silver(I) complexes of the formula [Ag2(L)2(CF3SO3)2] (1), [Ag2(L)2(CH3SO3)2] (2) [Ag2(L)2](BF4)2 (3), [Ag3(L)2(NO3)2]NO3·5H2O (4), [Ag2(L)(NO3)2]·CH3OH (5), [Ag2(L)2](ClO4)2 (6) and [Ag3(L)2(CH3CN)3](ClO4)3 (7) have been synthesized by reactions of 1,3,5-tris(2-oxazolinyl)benzene (L) with varied silver(I) salts under different conditions. The influences of counter anions and reaction conditions on the structure of the complexes are discussed. Three complexes 1, 2 and 3 with two kinds of different 1D chain structures were obtained under the same synthetic conditions by using different silver(I) salts, and the ligand L was found to adopt bis-monodentate (1 and 2) and tris-monodentate (3) coordination modes respectively. On the other hand, by using the same silver(I) nitrate or silver(I) perchlorate but different reaction solvents, 4 and 5 or 6 and 7 were isolated respectively. Complexes 4 and 5 have different 1D chain structures, and 6 is isostructural with 3. However, 7 is a tri-nuclear, propeller-shaped M3L2 supramolecular capsule in which L adopts a cis,cis,cis-conformation, while the ligand L in 3–6 has cis,trans,trans-conformation. The results revealed that the nature of the counter anions, such as their size, coordination ability and coordination mode, and the reaction conditions all have great impact on the structure of the complexes. The complexes were also characterized by electrospray mass spectrometry. Furthermore, complex 7 exhibited modest second-harmonic-generation (SHG) efficiency.
Co-reporter:Guang-Xiang Liu, Yong-Qing Huang, Qian Chu, Taka-aki Okamura, Wei-Yin Sun, Hong Liang and Norikazu Ueyama
Crystal Growth & Design 2008 Volume 8(Issue 9) pp:3233-3245
Publication Date(Web):July 17, 2008
DOI:10.1021/cg701137d
This work presents a systematic investigation on reactions of a flexible tricarboxylic acid with Zn(II), Cd(II) in the presence of varied N-donor ancillary ligands. Seven new metal−organic frameworks [Zn3(bta)2(bpy)2] (1), [Zn3(bta)2(dpe)2]·2H2O (2), [Zn2(OH)(bta)(bpe)]·2H2O (3), [Zn2(OH)(bta)(bpp)] (4), [Cd2(bta)(bpy)2(H2O)]ClO4·H2O (5), [Cd3(bta)2(bpy)2]·2H2O (6), and [Cd3(bta)2(H2O)2] (7) [bta3− = benzene-1,3,5-triacetate, bpy = 4,4′-bipyridine, dpe = 1,2-di(4-pyridyl)ethylene, bpe = 1,2-bis(4-pyridyl)ethane, and bpp = 1,3-bis(4-pyridyl)propane] have been obtained and characterized by single-crystal X-ray diffraction, IR, thermogravimetric and elemental analyses. Complexes 1−3, 5, and 6 are three-dimensional (3D) architectures containing infinite two-dimensional (2D) networks pillared by N-donor ligands, whereas 4shows 2D network structure. Complex 3 has 2-fold interpenetration of 3D frameworks with 4.82 networks linked by bpe ligands, and 5 features an unusual 3D cationic supramolecular architecture. Complex 7 contains the Kagomé lattice inorganic layers, which are further linked by bta3− ligands to form a 3D supramolecular architecture. The results showed that the structure and flexibility of the N-donor ancillary ligands have great influence on the structure of the complexes. The photoluminescence properties of 1−7 in the solid-state at room temperature have been studied.
Co-reporter:Guan-Cheng Xu, Yu-Jie Ding, Yong-Qing Huang, Guang-Xiang Liu, Wei-Yin Sun
Microporous and Mesoporous Materials 2008 Volume 113(1–3) pp:511-522
Publication Date(Web):1 August 2008
DOI:10.1016/j.micromeso.2007.12.012
Flexible tripodal ligand 1,3,5-tris(imidazol-1-ylmethyl)benzene (L) was used to react with various zinc(II) salts ZnX [X = (BF4)2, SO4, Cl2, Br2, I2] to afford a series of coordination polymers with different structures. {[Zn(L)2](BF4)2}n (1) has an infinite 2D cationic double layered structure, while {[Zn4(L)3(SO4)4] · 9H2O}n (2) possesses a 3D framework structure with two different kinds of channels. The structure of [Zn3(L)2Cl6]n (3) is 2D network and the one of {[Zn3(L)2Br6] · CH3OH}n (4) is an infinite 1D zigzag chain in a plywood-like stacking fashion. {[Zn(L)I]I}n (5) has 2D network structure which is further linked by hydrogen bonds to give rise to a fascinating 3D interlocked framework with twofold interpenetration. The results demonstrated that the counteranions have drastic effects on the structure of the coordination polymers. On the other hand, the flexible ligand L acts as a three-connecting node to connect three zinc(II) centers with different conformations. In 1 and 5, L has cis, cis, cis-conformation, while in 2, it adopts cis, trans, trans-conformation. It is interesting that two different conformations (cis, cis, cis and cis, trans, trans) of L coexist in 3 and in the case of 4, the ligand L adopts a special trans-conformation. The results attest that the flexible ligand L can adopt different conformations to form complexes with varied structures. In addition, the uncoordinated tetrafluoroborate anions in 1 can be exchanged by nitrate or nitrite anions, which mean that 1 has anion exchange property.
Co-reporter:Zhao-Peng Qi, Shu-An Li, Yong-Qing Huang, Guan-Cheng Xu, Guang-Xiang Liu, Ling-Yan Kong, Wei-Yin Sun
Inorganic Chemistry Communications 2008 Volume 11(Issue 8) pp:929-934
Publication Date(Web):August 2008
DOI:10.1016/j.inoche.2008.05.006
Two novel zinc(II) coordination complexes [Zn2(L)(CO3)]Br2 · 7H2O (1) and [Zn2(L)(CO3)]Br2 · 0. 5CH3COCH3 · 5H2O (2) with new macrocyclic ligand 3, 6, 9, 12, 20, 23, 26, 29-octaazatricyclo[29.3.1.114,18] hexatriaconta-1(34), 14, 16, 18(36), 31(35), 32-hexaene (L) were synthesized at an initial pH of ca. 9.5 with evaporation and diffusion methods, respectively. The dinuclear units of [Zn2(L)]4+ in both complexes are linked together by carbonate anions to form 1D infinite chain structure. The results show that carbon dioxide from air was absorbed and converted to carbonate anion in the formation of complexes 1 and 2. To the best of our knowledge, this is the first example of absorption and hydration of atmosphere carbon dioxide to form the 1D chain structure in the zinc(II) macrocyclic complexes.Two novel zinc(II) coordination complexes [Zn2(L)(CO3)]Br2 · 7H2O (1) and [Zn2(L)(CO3)]Br2 · 0.5CH3COCH3 · 5H2O (2) with 1D chain structure linked by carbonate anions were obtained by reactions of new macrocyclic ligand 3, 6, 9, 12, 20, 23, 26, 29-octaazatricyclo[29.3.1.114,18]hexatriaconta-1(34), 14, 16, 18(36), 31(35), 32-hexaene (L) with zinc salt at an initial pH of ca. 9.5. The results show that carbon dioxide from air was absorbed and converted to carbonate anion during the formation of 1 and 2.
Co-reporter:Zheng-Shuai Bai, Guang-Xiang Liu, Yi Lu, Wei-Yin Sun
Inorganic Chemistry Communications 2008 Volume 11(Issue 5) pp:513-517
Publication Date(Web):May 2008
DOI:10.1016/j.inoche.2008.02.004
Two novel inorganic–organic hybrid frameworks [Cu2(BPTCA)(H2O)2 · 2H2O]n (1) and [Cd2(BPTCA)(μ-OH2)2]n (2) were obtained by reactions of 4,4′-bipyridine-2,2′,6,6′-tetracarboxylic acid (H4BPTCA) with copper(II) and cadmium(II) salts, respectively and characterized by X-ray single crystal structure analysis. Complex 1 has a two-dimensional ladder-like structure containing infinite –Cu–O– chains. The magnetic susceptibility data of 1 show the intra-chain ferromagnetic exchange coupling resulting from the orthogonal arrangement of copper magnetic orbital within the –Cu–O– infinite chain. Complex 2 is a three-dimensional framework in which the –Cd–(O)2– zigzag-chains are linked by BPTCA4−. The photoluminescence property of 2 is studied.Two novel frameworks [Cu2(BPTCA)(H2O)2 · 2H2O]n (1) and [Cd2(BPTCA)(μ2-OH2)2]n (2) with two-dimensional ladder-like and three-dimensional structures were obtained by reactions of 4,4′-bipyridine-2,2′,6,6′-tetracarboxylic acid (H4BPTCA) with copper(II) and cadmium(II) salts, respectively. The magnetic susceptibility data of 1 show the intra-chain ferromagnetic exchange coupling within the –Cu–O– infinite chain.
Co-reporter:Qian Chu, Guang-Xiang Liu, Yong-Qing Huang, Xiao-Feng Wang and Wei-Yin Sun
Dalton Transactions 2007 (Issue 38) pp:4302-4311
Publication Date(Web):08 Aug 2007
DOI:10.1039/B707159K
Five novel coordination polymers [Zn2(OA)(4,4′-bipy)(H2O)]·0.5(4,4′-bipy) (1), [Zn2(OA)(dib)(H2O)]·H2O (2), [Zn2(OA)(bbi)2]·3H2O (3), [Zn2(OA)(phen)2(H2O)] (4) and [Zn4(OA)2(2,2′-bipy)2(H2O)]·2H2O (5) were obtained by hydrothermal reactions of Zn(NO3)2·6H2O with a V-shaped multicarboxylate ligand 3,3′,4,4′-oxydiphthalic acid (H4OA) and a series of N-donor ligands, namely 4,4′-bipyridine (4,4′-bipy), 1,4-di(1-imidazolyl)benzene (dib), 1,1′-(1,4-butanediyl)bis(imidazole) (bbi), 1,10-phenanthroline (phen), 2,2′-bipyridine (2,2′-bipy). The structures of the complexes were established by single-crystal X-ray diffraction analysis. Complex 1 exhibits a robust 3D porous structure with uncoordinated 4,4′-bipy molecules filling the cavities. Complexes 2 and 5 show a complicated 3D framework, while complexes 3 and 4 have a 2D network and a 1D helical chain structure, respectively. The results indicate that the multicarboxylate OA4− ligand can adopt varied coordination modes in the formation of the complexes and the influence of the N-donor ligand on the structure of the complexes is discussed. The photoluminescence properties of H4OA and 1–5 were studied in the solid state at room temperature. Moreover, nonlinear optical measurements showed that 5 displayed a second-harmonic-generation (SHG) response of 0.5 times of that for urea. The results suggested that the configuration and flexibility of the ligands play a key role in directing the related properties of the complexes.
Co-reporter:Ling-Yan Kong, Xi-Hong Lu, Yong-Qing Huang, Hiroyuki Kawaguchi, Qian Chu, Hui-Fang Zhu, Wei-Yin Sun
Journal of Solid State Chemistry 2007 Volume 180(Issue 1) pp:331-338
Publication Date(Web):January 2007
DOI:10.1016/j.jssc.2006.10.029
Three novel coordination polymers [Cd3(L)2(μ-Br)(μ-Cl)Br3Cl] (1), [Cd3(L)2(μ-Cl)2Cl4] (2) and [Cd(L)Cl]2[CdCl4]·H2O (3) were obtained by reactions of an imidazole-containing tripodal ligand N1-(2-aminoethyl)-N1-(2-imidazolethyl)-ethane-1,2-diamine (L) with Cd(II) salts. Their structures were determined by X-ray crystallography. Crystal data for 1, monoclinic system, P21/c, a=7.752(4) Å, b=31.70(2) Å, c=14.012(7) Å, β=109.439(7)°, V=3247(3) Å3, Z=4. 2, monoclinic system, P21/c, a=7.6564(15) Å, b=31.433(6) Å, c=13.925(3) Å, β=109.89(3)°, V=3151.1(11) Å3, Z=4. 3, orthorhombic system, Pbcn, a=22.950(2) Å, b=8.435(7) Å, c=17.360(2) Å, V=3360.3(51) Å3, Z=4. Complexes 1 and 2 have similar one-dimensional (1D) branched-chain structure while complex 3 features a 1D zigzag cationic chain with [CdCl4]2− serving as counter anion. The photoluminescent measurements reveal that all the complexes exhibit blue fluorescence at room temperature in the solid state.Three novel coordination polymers [Cd3(L)2(μ-Br)(μ-Cl)Br3Cl] (1), [Cd3(L)2(μ-Cl)2Cl4] (2) and [Cd(L)Cl]2[CdCl4]·H2O (3) with one dimensional branched chain and zigzag chain structures were obtained by reactions of an imidazole-containing tripodal ligand N1-(2-aminoethyl)-N1-(2-imidazolethyl)-ethane-1,2-diamine (L) with Cd(II) salts.
Co-reporter:Gang Wu;Yan Wang;Xiao-Feng Wang
Journal of Chemical Crystallography 2007 Volume 37( Issue 3) pp:199-205
Publication Date(Web):2007 March
DOI:10.1007/s10870-006-9164-7
Two complexes (H2bipy)[M2(TB)2(H2O)8]·5H2O (M = Mn 1, Zn 2) (bipy = 4,4′-bipyridine, H3TB = 1,3,5-tris(carboxymethoxyl)benzene) were synthesized by the reaction of the corresponding metal salt with ligand H3TB and 4,4′-bipy in an aqueous methanol solution at room temperature, respectively. Their structures were determined by single crystal X-ray diffraction analysis. Both complexes 1 and 2 crystallize in the triclinic space group \(P\bar 1\) with the crystal parameters of 1: a = 9.725(12) Å, b = 10.651(13) Å, c = 10.882(13) Å, α = 91.72(2)°, β = 96.41(2)°, γ = 97.72(2)°, V = 1109(2) Å3, Z = 1 and 2: a = 9.610(10) Å, b = 10.55(2) Å, c = 10.83(2) Å, α = 91.60(4)°, β = 95.32(2)°, γ = 97.73(4)°, V = 1082(3) Å3, Z = 1. Complexes 1 and 2 have the same dinuclear structure, in which each metal atom is six coordinated with distorted octahedral geometry by two oxygen atoms from two different TB3− ligands and four ones from four coordinated water molecules. The dinuclear units are further linked by hydrogen bonding and π–π interactions to form the three-dimensional framework structure.
Co-reporter:Yan Wang;Yong-Qing Huang;Guang-Xiang Liu;Taka-aki Okamura Dr.;Mototsugu Doi;Yue-Wei Sheng Dr.;Norikazu Ueyama
Chemistry - A European Journal 2007 Volume 13(Issue 26) pp:
Publication Date(Web):21 JUN 2007
DOI:10.1002/chem.200700133
Five novel transition metal complexes [CdII3(tpba-2)2(SCN)6]⋅6 THF⋅3 H2O (1), [CuII3(tpba-2)2(SCN)6]⋅6 THF⋅3 H2O (2), [NiII3(tpba-2)2(SCN)6]⋅6 THF⋅3 H2O (3), [CdII2(tpba-2)(SCN)3]ClO4 (4), [CuI3(SCN)6(H3tpba-2)] (5) [TPBA-2 = N′,N′′,N′′′-tris(pyrid-2-ylmethyl)-1,3,5-benzenetricarboxamide, THF=tetrahydrofuran] were obtained by reactions of the corresponding transition metal salts with TPBA-2 ligand in the presence of NH4SCN using layering or solvothermal method, respectively. The results of X-ray crystallographic analysis showed that complexes 1, 2 and 3 are isostructural and have the same 2D honeycomb network structure with Kagomé lattice, in which all the MII (M = Cd, Cu, Ni) atoms are six-coordinated, and the TPBA-2 ligands adopt cis,cis,cis conformation while the thiocyanate anions act as terminal ligands. Capsule-like motifs are found in 1, 2 and 3, in which six THF molecules are hosted, and the results of XPRD and solid-state 13C NMR spectral measurements showed that the compound 1 can selectively desorb and adsorb THF molecules occurring along with the re-establishment of its crystallinity. In contrast to 1, 2 and 3, complex 4 has different 2D network structure, resulting from TPBA-2 ligands with cis,trans,trans conformation, thiocyanate anions serving as end-to-end bridging ligands, and the incomplete replacement of perchlorate anions, which further link the 2D layers into 3D framework by the hydrogen bonds. In complex 5, the CuII atoms are reduced to CuI during the process of solvothermal reaction, and the CuI atoms are connected by thiocyanate anions to form a 3D porous framework, in which the protonated TPBA-2 ligands are hosted in the cavities as templates.
Co-reporter:Ling-Yan Kong, Hui-Fang Zhu, Taka-aki Okamura, Yu-Hua Mei, Wei-Yin Sun, Norikazu Ueyama
Journal of Inorganic Biochemistry 2006 Volume 100(Issue 7) pp:1272-1279
Publication Date(Web):July 2006
DOI:10.1016/j.jinorgbio.2006.02.020
An imidazole-containing tripodal polyamine ligand N1-(2-aminoethyl)-N1-(2-imidazol-1-ylethyl)-ethane-1,2-diamine (L) was prepared and its dinuclear zinc(II) complex [Zn(L)(H2O)]2(ClO4)4 · 4 H2O (1) was obtained and examined as a catalyst for the hydrolysis of 4-nitrophenyl acetate (NA). X-ray crystal structure analysis of the complex revealed that the complex features a dinuclear cation unit with a Zn ⋯ Zn distance of 8.34 Å and both Zn(II) centers adopt distorted trigonal-bipyramid geometry. The solution complexation investigation performed at 25 °C by means of potentiometric titration revealed that the mononuclear species [ZnL]2+ is predominating in the pH rage of 7.0–9.7 in the solution and the pKa1 for the Zn-bound water is 8.50 ± 0.01. Complex 1 promoted hydrolysis of NA showed a second-order rate constant of 0.046 ± 0.004 M−1 s−1 at pH 9.0 in 10% (v/v) CH3CN aqueous solution at 25 °C. The pH-rate profile for the second-order rate constant of NA hydrolysis with complex 1 gave a sigmoidal curve. And the results show that in the hydrolysis process the two Zn(II) centers of the dinuclear deprotonated species do not cooperate with each other and the Zn-bound hydroxide servers as reactive nucleophile toward the ester.
Co-reporter:Wen-Li Meng;Zheng-Hua Zhang;Yang Lv;Hiroyuki Kawaguchi
Applied Organometallic Chemistry 2006 Volume 20(Issue 6) pp:
Publication Date(Web):15 MAY 2006
DOI:10.1002/aoc.1073
A new complex [Pr(bib)2(NO3)3] (1) was synthesized by reaction of bidentate imidazole-containing ligand 1-bromo-3,5-bis(imidazol-1-ylmethyl)benzene (bib) with Pr(NO3)·6H2O and characterized by X-ray crystallography. Complex 1 has a two-dimensional herringbone-like structure with the ligand bib serving as a bridging ligand using its two imidazolyl nitrogen atoms. Ligand bib adopts cis and trans two different conformations, and the Pr(III) atoms are bridged by bib in two different ways. Thermogravimetric analysis for complex 1 was carried out and the result shows that the complex is stable up to 180 °C. Variable-temperature magnetic susceptibility of complex 1 was measured between 1.8 and 300 K and the result shows that the χMT value decreases continuously over the whole temperature range. Copyright © 2005 John Wiley & Sons, Ltd.
Co-reporter:Wei Zhao, Jian Fan, You Song, Hiroyuki Kawaguchi, Taka-aki Okamura, Wei-Yin Sun and Norikazu Ueyama
Dalton Transactions 2005 (Issue 8) pp:1509-1517
Publication Date(Web):22 Mar 2005
DOI:10.1039/B419418G
Three novel metal–organic frameworks (MOFs), [Cu(1)SO4]·H2O (4), [Cu2(2)2(SO4)2]·4H2O (5) and [Cu(3)(H2O)]SO4·5.5H2O (6), were obtained by hydrothermal reactions of CuSO4·5H2O with the corresponding ligands, which have different flexibility. The structures of the synthesized complexes were determined by single-crystal X-ray diffraction analyses. Complex 4 has a 2D network structure with two types of metallacycles. Complex 5 also has a 2D network structure in which each independent 2D sheet contains two sub-layers bridged by oxygen atoms of the sulfate anions. Complex 6 has a 2D puckered structure in which the sulfate anions serve as counter anions, which are different from those in complexes 4
(terminators) and 5
(bridges). The different structures of complexes 4, 5 and 6 indicate that the nature of organic ligands affected the structures of the assemblies greatly. The magnetic behavior of complex 5 and anion-exchange properties of complex 6 were investigated.
Co-reporter:Wei Zhao, Jian Fan, Taka-aki Okamura, Wei-Yin Sun, Norikazu Ueyama
Microporous and Mesoporous Materials 2005 Volume 78(2–3) pp:265-279
Publication Date(Web):1 March 2005
DOI:10.1016/j.micromeso.2004.10.030
Six novel coordination polymers, [Cu(tib)2(N3)2] · 2H2O (1), [Cd(tib)2(H2O)2](NO3)2 (2), [Cu(dien)(tib)](ClO4)2 · tib · CH3CN (3), [Mn(ibimb)2(H2O)2]Cl2 · 2H2O (4), [Zn(titmb)2](NO3)2 · 2MeOH (5) and [Cd3(titmb)2Br6] (6), where tib = 1,3,5-tris(1-imidazolyl)benzene, dien = diethylenetriamine, ibimb = 1-(1-imidazolyl)-3,5-bis(imidazol-1-ylmethyl)benzene, titmb = 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene, were obtained by self-assembly of tripodal ligands with the corresponding metal salts, and their structures were determined by single crystal X-ray diffraction analyses. Complexes 1 and 2 have similar 2D network structure in which only two of three imidazole groups of each tib ligand coordinated to the metal atoms and the additional one did not participate in the coordination. Complex 3 has a 1D chain structure in which there are two kinds of tib ligands, one kind of tib serves as a two-connecting (bridging) ligand using its two arms. The other kind of tib acts as guest molecule filled in the void of cationic 1D chains. Complex 4 has an infinite 1D hinged chain structure and ligand ibimb serves as a two-connecting (bridging) ligand using its two flexible arms. Complex 5 has a 2D honeycomb network structure with (6,3) topology in which titmb acts as a three-connecting ligand. Complex 6 has an infinite 1D chain structure in which each titmb ligand connects three metal atoms. Ligand titmb has cis, trans, trans-conformation in 6, which is different from that in complex 5(cis, cis, cis). The anion-exchange properties of complex 5 were investigated.
Co-reporter:Bin Sui, Jian Fan, Taka-aki Okamura, Wei-Yin Sun, Norikazu Ueyama
Solid State Sciences 2005 Volume 7(Issue 8) pp:969-982
Publication Date(Web):August 2005
DOI:10.1016/j.solidstatesciences.2004.11.005
Two coordination polymers with M2L2 type metallocyclic rings [Mn(dimb)2(NCS)2]n (1) and [Mn(dimb)2(N3)2]n (2) were synthesized by reactions of bidentate ligand containing imidazole donors, namely 1,3-bis(imidazol-1-ylmethyl)-5-methylbenzene (dimb), with the manganese(II) salts. While the bimb ligand reacts with Zn(NO3)2⋅6H2O and NaN3 or AgClO4, complexes [Zn(dimb)2(N3)2]n (3) and {[Ag(dimb)]ClO4}n (4) with one-dimensional chain structure were obtained. When the ligand dimb reacted with Cu(NO3)2⋅3H2O, a two-dimensional network {[Cu(dimb)2(H2O)2](NO3)2}n (5) was achieved, in which the metal atoms had octahedral coordination geometry. The structures of these coordination complexes were determined by X-ray crystallography and the results revealed that both coordination geometry of metal atoms and conformation of ligand have great impacts on the structure of the supramolecular architectures. Magnetic properties of Mn(II) complexes were also investigated.
Co-reporter:Ling-Yan Kong, Zhen-Wu Li, Taka-aki Okamura, Guo-Hong Ma, Qian Chu, Hui-Fang Zhu, Sing-Hai Tang, Wei-Yin Sun, Norikazu Ueyama
Chemical Physics Letters 2005 Volume 416(1–3) pp:176-181
Publication Date(Web):29 November 2005
DOI:10.1016/j.cplett.2005.09.074
Abstract
Three coordination polymers [Co(L)2(SCN)2] (1), [Mn(L)2(SCN)2] (2) and [Cd(H4L)2Cl2] (3), were obtained by the reaction of CoII, MnII, CdII salts with di-Schiff base ligand N,N′-bis(3-pyridylmethyl)-4,4′-biphenylenedimethyleneimine (L) and its reduced form (H4L), respectively and their structures were determined by X-ray crystallography. In the solid state, complexes 1 and 2 feature 1D hinged chains, while complex 3 has a 2D network structure. Complex 2 was found to show optical limiting property with a 3 ns pulsed laser at 532 nm in DMF solution.
Co-reporter:Ling-Yan Kong;Zheng-Hua Zhang;Hui-Fang Zhu Dr.;Hiroyuki Kawaguchi Dr.;Taka-aki Okamura Dr.;Mototsugu Doi;Qian Chu Dr.;Norikazu Ueyama Dr.
Angewandte Chemie International Edition 2005 Volume 44(Issue 28) pp:
Publication Date(Web):17 JUN 2005
DOI:10.1002/anie.200500587
Carbonato bridges from atmospheric carbon dioxide: The copper(II) and zinc(II) complexes of the novel imidazole-containing polyamine ligand N1-(2-aminoethyl)-N1-(2-imidazolethyl)ethane-1,2-diamine are found to fix carbon dioxide by hydration to μ3-carbonate ligands. This is revealed by IR and solid-state 13C NMR spectroscopic and X-ray crystallographic studies of the two-dimensional complexes (see picture).
Co-reporter:Ling-Yan Kong;Zheng-Hua Zhang;Hui-Fang Zhu Dr.;Hiroyuki Kawaguchi Dr.;Taka-aki Okamura Dr.;Mototsugu Doi;Qian Chu Dr.;Norikazu Ueyama Dr.
Angewandte Chemie 2005 Volume 117(Issue 28) pp:
Publication Date(Web):17 JUN 2005
DOI:10.1002/ange.200500587
Carbonatbrücken aus atmosphärischem Kohlendioxid: Die Kupfer(II)- und Zink(II)-Komplexe des neuartigen Imidazol-haltigen Polyaminliganden N1-(2-Aminoethyl)-N1-(2-imidazolethyl)ethan-1,2-diamin binden Kohlendioxid durch Hydratisierung zu μ3-Carbonatliganden. Dies ergaben IR- und Festkörper-13C-NMR-spektroskopische sowie röntgenographische Untersuchungen der zweidimensionalen Komplexe (siehe Bild).
Co-reporter:Hui-Fang Zhu, Wei Zhao, Taka-aki Okamura, Jian Fan, Wei-Yin Sun and Norikazu Ueyama
New Journal of Chemistry 2004 vol. 28(Issue 8) pp:1010-1018
Publication Date(Web):15 Jul 2004
DOI:10.1039/B315842J
Reactions of a new asymmetric ligand, 1-(1-imidazolyl)-4-(imidazol-1-ylmethyl)benzene (IIMB), with various metal [Cd(II), Mn(II), Zn(II)] salts led to the formation of molecular, one- (1D) and two-dimensional (2D) architectures [Cd(IIMB)2(H2O)(SO4)]·7.5H2O 1, [Cd(IIMB)2Cl2]·H2O 2, [Cd(IIMB)4(H2O)2](NO3)2·5H2O 3, [Cd(IIMB)(OAc)2]·H2O 4, [Mn(IIMB)2(SO4)(H2O)]·8.2H2O 5, [Mn(IIMB)4(H2O)2]Cl2·5H2O 6 and [Zn(IIMB)2]4(NO3)8·13.5H2O 7. All the structures were established by single-crystal X-ray diffraction analysis. Both compounds 1 and 5 with sulfate anion are 2D polycatenanes formed by the interlocking of 1D double-stranded chains, while 2 and 4 with chloride and acetate anions are 1D chains. The results provide nice examples of topologies of metal-organic frameworks controlled by the counter anions. Interestingly, 3 and 6 are discrete molecular complexes with monometallic cores and form 2D networks through strong intermolecular hydrogen bonds. Complex 7, obtained under the same conditions as 3, is a 1D tubular chain. The structural difference between 3 and 7 suggests the metal ions also have a significant effect on the construction of supramolecular architectures. Furthermore, the photoluminescence properties of these compounds were investigated in the solid state at room temperature.
Co-reporter:Hui-Fang Zhu;Ling-Yan Kong;Taka-aki Okamura;Jian Fan;Norikazu Ueyama
European Journal of Inorganic Chemistry 2004 Volume 2004(Issue 7) pp:
Publication Date(Web):26 FEB 2004
DOI:10.1002/ejic.200300623
Four new coordination frameworks {[Ag2(L1)](NO3)2·2H2O}n (1), {[Ag(L1)](CF3COO)·2.5H2O}n (2), {[Ag2(L1)2][1,4-C6H4(COO)2]·7H2O}n (3) and {[Ag(L1)]ClO4}n (4) were obtained by the reaction of N,N′-bis(3-pyridylmethyl)-1,4-benzenebis(methylamine) (L1) with the corresponding silver(I) salts. X-ray diffraction analyses reveal that complex 1 has an infinite 1D chain structure, in which L1 acts as a tetradentate ligand. Complexes 2, 3 and 4 have 2D network structures, and the L1 ligands in these complexes adopt two different coordination modes: one kind of ligand coordinates four silver(I) atoms using its four N atoms, and the other kind of ligand connects only two silver(I) atoms with the two N atoms of the benzenebis(methylamine) unit, while the pyridine units remain free of coordination. Complex {[Ag(L2)]ClO4}n (5) was synthesized by reaction of N,N′-bis(3-pyridylmethyl)-1,4-benzenebis(methyleneamine) (L2) with silver(I) perchlorate. It has a novel 1D chain structure, which is different from that of 4 due to the different flexibility of the ligands L1 and L2. All of these complexes form 2D or 3D structures stabilized by hydrogen bonding, C−H···π and π-π interactions. The results revealed that the nature of the counteranions and the flexibility of the ligand have an impact on the structure of the supramolecular architectures. The complexes were also characterized by electrospray mass spectrometry. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Co-reporter:Shuang-Yi Wan, Yu-Ting Huang, Yi-Zhi Li, Wei-Yin Sun
Microporous and Mesoporous Materials 2004 Volume 73(1–2) pp:101-108
Publication Date(Web):6 August 2004
DOI:10.1016/j.micromeso.2003.12.029
Novel polymeric coordination complex [Ni(timpt)2](ClO4)21 was synthesized by solvothermal reaction of 2,4,6-tris[4-(imidazol-1-ylmethyl)phenyl]-1,3,5-triazine (timpt) ligand with Ni(ClO4)2 · 6H2O and characterized by X-ray crystallography. Each Ni(II) is coordinated by six imidazolyl N atoms from six different timpt ligands with an octahedral geometry and each timpt ligand connects three metal atoms to generate a three-dimensional (3D) metal-organic framework with self-penetration. The uncoordinated perchlorate anions are located within the voids of the 3D structure through C–H⋯O hydrogen bonds, which enable the complex to show anion-exchange property.
Co-reporter:Ling-Yan Kong, Hui-Fang Zhu, Taka-aki Okamura, Wei-Yin Sun, Norikazu Ueyama
Journal of Solid State Chemistry 2004 Volume 177(Issue 7) pp:2271-2280
Publication Date(Web):July 2004
DOI:10.1016/j.jssc.2004.03.005
Five novel coordination polymers, [Co(bpb)2Cl2] (1), [Co(bpb)2(SCN)2] (2), [Cd(H4bpb)0.5(dmf)(NO3)2] (3), [Cd2(H4bpb)Br4] (4), and [Hg2(H4bpb)I4] (5) [bpb=N,N′-bis(3-pyridylmethyl)-1,4-benzenedimethyleneimine, H4bpb=N,N′-bis(3-pyridylmethyl)-1,4-benzenedimethylamine], were synthesized and their structures were determined by X-ray crystallography. In the solid state, complex 1 is a 1D hinged chain, while 2 has 2D network structure with the ligand bpb serving as a bridging ligand using its two pyridyl N atoms. The imine N atoms keep free of coordination and bpb acts as a bidentate ligand in both 1 and 2. Complexes 3, 4, and 5 with reduced bpb ligand, i.e. H4bpb, show similar 2D network structure, in which ligand H4bpb serves as a tetradentate ligand. Thermogravimetric analyses for complexes 1–5 were carried out and found that they have high thermal stability. The magnetic susceptibilities of compounds 1, 2 were measured over a temperature range of 75–300 K.
Co-reporter:Jian Fan, Wei-Yin Sun, Taka-aki Okamura, Wen-Xia Tang, Norikazu Ueyama
Inorganica Chimica Acta 2004 Volume 357(Issue 8) pp:2385-2389
Publication Date(Web):10 June 2004
DOI:10.1016/j.ica.2004.01.003
The reaction between 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (titmb) and [Ag(NH3)2][Hsal] (H2sal=salicylic acid) produces novel complex [Ag2(titmb)2][Hsal]2 · 3H2O (1). There are two unique silver centers in complex 1 with one serving as a trigonal node and the other one as a linear node. Interestingly, there are two sorts of titmb ligands in complex 1, one acting as a three-connecting ligand and the other one as a two-connecting (bridging) ligand. The silver centers are linked by titmb ligand to form 2D puckered layers containing M5(titmb)5 macrocyclic motifs, which is large enough to allow the bridging titmb ligands from the neighboring layers to be completely enclosed in. Namely, two neighboring independent layers interpenetrated each other in a parallel fashion without the occurrence of catenation to give a 3D structure.A novel 2D silver(I) coordination polymer with 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene was prepared and characterized by X-ray determination. The neighboring 2D layers interpenetrated each other without the occurrence of catenation to generate the 3D structure.
Co-reporter:Jian Fan, Mou-Hai Shu, Taka-aki Okamura, Yi-Zhi Li, Wei-Yin Sun, Wen-Xia Tang and Norikazu Ueyama
New Journal of Chemistry 2003 vol. 27(Issue 9) pp:1307-1309
Publication Date(Web):24 Jul 2003
DOI:10.1039/B306876P
Reaction of 1,3,5-tris(1-imidazolyl)benzene with Pb(NO3)2 in DMF affords a novel metal-organic framework with 4.82 topology in which the DMF molecules are attached to the channel walls, while in the reaction carried out in methanol, a one-dimensional coordination polymer was obtained.
Co-reporter:Xing-Mei Ouyang;Bao-Li Fei;Taka-aki Okamura;Hong-Wei Bu;Wen-Xia Tang;Norikazu Ueyama
European Journal of Inorganic Chemistry 2003 Volume 2003(Issue 4) pp:
Publication Date(Web):29 JAN 2003
DOI:10.1002/ejic.200390084
Four novel two-dimensional coordination polymers [Ag2(L1)2](CF3SO3)2·H2O (1), [Ag3(L1)2](NO3)3·H2O (2), [Co(L1)2(SCN)2]·EtOH (3), and [Co(L2)2(SCN)2] (4) were obtained by reactions of the bis(Schiff base) ligand 1,2-bis(4′-pyridylmethyleneamino)ethane (L1) with silver(I) trifluoromethanesulfonate, silver(I) nitrate, and cobalt(II) thiocyanate, and 1,2-bis(3′-pyridylmethyleneamino)ethane (L2) with cobalt(II) thiocyanate, respectively. In complex 1, a 2D network structure was achieved by hydrogen bonding interactions between the two 1D chains, consisting of double-stranded helicates, through solvate water molecules. The 2D network of complex 2 was formed by the coordination to a two-coordinate silver(I) ion instead of hydrogen bonds as in complex 1. Complex 3 contains molecular square units, which are occupied by disordered ethanol molecules. Complex 4 exhibits a classic square-grid network which is different from that of 3 due to the different terminal pyridyl groups in L1 (4-pyridyl) and L2 (3-pyridyl). These coordination polymers were characterized by X-ray crystallography, electrospray mass spectrometry, cyclic voltammetry and magnetic measurements. The results show a 2D network superstructural diversity by the fine-tuning of construction components. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Co-reporter:Shuang-Yi Wan;Yi-Zhi Li;Taka-aki Okamura;Jian Fan;Norikazu Ueyama
European Journal of Inorganic Chemistry 2003 Volume 2003(Issue 20) pp:
Publication Date(Web):13 OCT 2003
DOI:10.1002/ejic.200300098
Two novel coordination networks, [Zn2(timpt)2(μ-OH)](NO3)3 (1) and [Ni2(timpt)2(H2O)2(SO4)2]·0.5H2O (2) were obtained by assembly of 2,4,6-tris[4-(imidazol-1-ylmethyl)phenyl]-1,3,5-triazine (timpt) with the corresponding metal salts. The X-ray single-crystal diffraction analysis reveals that complex 1 possesses μ-OH-bridged dinuclear zinc(II) subunits (Zn2OH) and each timpt ligand connects three metal atoms to form a two-dimensional (2D) honeycomb network structure, in which each independent sheet contains two sublayers. While in the case of complex 2, the nickel(II) atom is coordinated by N atoms of timpt, O atoms of sulfate anions and water molecules to give a 2D honeycomb network. The luminescence properties of timpt, 1 and 2 in the solid state were investigated at room temperature. The maximum emission wavelength of 1 is red-shifted by 17 nm compared with that of timpt. While complex 2 showed an emission with remarkably reduced intensity under the same conditions. The results imply that the metal ions have great influence on the structure and properties of the complexes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Co-reporter:Yan Wang, Xing-Mei Ouyang, Taka-aki Okamura, Wei-Yin Sun, Norikazu Ueyama
Inorganica Chimica Acta 2003 Volume 353() pp:68-74
Publication Date(Web):8 September 2003
DOI:10.1016/S0020-1693(03)00244-5
A new flexible tetradentate ligand 1,2-bis(3′-pyridylmethylamino)ethane (L) was synthesized and its coordination complexes with cadmium(II) and silver(I) salts were characterized by X-ray single crystal structure analysis. The structure of [Cd(L)](NO3)2·H2O (1) is an infinite zigzag chain in which the Cd(II) atom is octahedrally coordinated with N4O2 donor set. The complex [Ag3(L)2](CF3SO3)3 (2) has a different 1D chain structure, interestingly, containing two- and three-coordinated silver(I) atoms. The photofluorescence and electrospray mass spectrometry of complexes 1 and 2 were also investigated.A new flexible tetradentate ligand 1,2-bis(3′-pyridylmethylamino)ethane (L) was synthesized and its coordination complexes with cadmium(II) and silver(I) salts were characterized by X-ray single crystal structure analysis. The structure of [Cd(L)](NO3)2·H2O (1) is an infinite zigzag chain in which the Cd(II) atom coordinates with N4O2 donor set. The complex [Ag3(L)2](CF3SO3)3 (2) has a different 1D chain structure containing two- and three-coordinated silver(I) atoms.
Co-reporter:Jian Fan;Hui-Fang Zhu;Taka-aki Okamura Dr. Dr.;Wen-Xia Tang ;Norikazu Ueyama Dr.
Chemistry - A European Journal 2003 Volume 9(Issue 19) pp:
Publication Date(Web):26 SEP 2003
DOI:10.1002/chem.200305089
Complex [Ag(tpba)N3] (1) was obtained by reaction of novel tripodal ligand N,N′,N″-tris(pyrid-3-ylmethyl)-1,3,5-benzenetricarboxamide (TPBA) with [Ag(NH3)2]N3. While the reactions between 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (TITMB) and silver(I) salts with different anions and solvent systems give six complexes: [Ag3(titmb)2](N3)3⋅CH3OH⋅4 H2O (2), [Ag3(titmb)2](CF3SO3)2(OH)⋅5 H2O (3), [Ag3(titmb)2][Ag(NO3)3]NO3⋅H2O (4), [Ag3(titmb)2(py)](NO3)3⋅H2O (py=pyridine) (5), [Ag3(titmb)2(py)](ClO4)3 (6), and [Ag3(titmb)2](ClO4)3⋅CHCl3 (7). The structures of these complexes were determined by X-ray crystallography. The results of structural analysis of complexes 1 and 2, with the same azide anion but different ligands, revealed that 1 is a twofold interpenetrated 3D framework with interlocked cage-like moieties, while 2 is a M3L2 type cage-like complex with a methanol molecule inside the cage. Entirely different structure and topology between 1 and 2 indicates that the nature of organic ligands affected the structures of assemblies greatly. While in the cases of complexes 2–7 with flexible tripodal ligand TITMB, they are all discrete M3L2 type cages. The results indicate that the framework of these complexes is predominated by the nature of the organic ligand and geometric need of the metal ions, but not influenced greatly by the anions and solvents. It is interesting that there is a divalent anion [Ag(NO3)3]2− inside the cage 4 and an anion of ClO4− or NO3− spontaneously encapsulated within the cage of complexes 5, 6 and 7.
Co-reporter:Jian Fan;Lu Gan;Hiroyuki Kawaguchi Dr. Dr.;Kai-Bei Yu ;Wen-Xia Tang
Chemistry - A European Journal 2003 Volume 9(Issue 16) pp:
Publication Date(Web):7 AUG 2003
DOI:10.1002/chem.200204298
Six noninterpenetrating organic–inorganic hybridized coordination complexes, [Mn(3)2(H2O)2](ClO4)2⋅2 H2O (5), [Mn(3)2(H2O)2](NO3)2 (6), [Mn(3)2(N3)2]⋅2 H2O (7), [Cu(3)2(H2O)2](ClO4)2 (8), [Mn(4)2(H2O)(SO4)]⋅CH3OH⋅5 H2O (9) and [Mn(4)2](ClO4)2 (10) were obtained through self-assembly of novel tripodal ligands, 1,3,5-tris(1-imidazolyl)benzene (3) and 1,3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene (4) with the corresponding metal salts, respectively. Their structures were determined by X-ray crystallography. The results of structural analysis of complexes 5, 6, 7, and 8 with rigid ligand 3 indicate that their structures are mainly dependant on the nature of the organic ligand and geometric need of the metal ions, but not influenced greatly by the anions and metal ions. While in complexes 9 and 10, which contain the flexible ligand 4, the counteranion plays an important role in the formation of the frameworks. Entirely different structures of complexes 5 and 10 indicate that the organic ligands greatly affect the structures of assemblies. Furthermore, in complexes 5 and 6, the counteranions located between the cationic layers can be exchanged by other anions. Reversible anion exchanges between complexes 5 and 6 without destruction of the frameworks demonstrate that 5 and 6 can act as cationic layered materials for anion exchange, as determined by IR spectroscopy, elemental analyses, and X-ray powder diffraction.
Co-reporter:Shuang-Yi Wan, Jian Fan, Taka-aki Okamura, Hui-Fang Zhu, Xing-Mei Ouyang, Wei-Yin Sun and Norikazu Ueyama
Chemical Communications 2002 (Issue 21) pp:2520-2521
Publication Date(Web):03 Oct 2002
DOI:10.1039/B207568G
Reaction of nanometer-sized tripodal ligand 2,4,6-tris[4-(imidazol-1-ylmethyl)phenyl]-1,3,5-triazine (timpt) with lead(II) nitrate affords a novel polycatenated structure containing three interpenetrating 4.82 networks, in which the lead(II) atom has a hemidirected coordination geometry and a stereochemically active lone pair of electrons.
Co-reporter:Jian Fan, Wei-Yin Sun, Taka-aki Okamura, Jin Xie, Wen-Xia Tang and Norikazu Ueyama
New Journal of Chemistry 2002 vol. 26(Issue 2) pp:199-201
Publication Date(Web):06 Feb 2002
DOI:10.1039/B109141G
A novel complex [Ag3(titmb)2]2[1,4-C6H4(COO)2]3·23 H2O [titmb=1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene] contains two M3L2 cages and three terephthalate anions, one of which is embedded in the two cages to form a dumbbell-like architecture and shows photoluminescence in the solid state when the titmb reacts with [Ag(NH3)2]NO3, an individual M3L2 cage [Ag3(titmb)2][NO3]3·5 H2O without luminescent properties was obtained.
Co-reporter:Hui-Fang Zhu, Wei Zhao, Taka-aki Okamura, Bao-Li Fei, Wei-Yin Sun and Norikazu Ueyama
New Journal of Chemistry 2002 vol. 26(Issue 10) pp:1277-1279
Publication Date(Web):20 Aug 2002
DOI:10.1039/B200383J
A novel snake-like zinc(II) coordination polymer with blue photoluminescence, {[Zn(bimb)(OAc)2]·6H2O}∞
[bimb=4,4′-bis(imidazol-1-ylmethyl)biphenyl, OAc=acetate anion], was obtained by reaction of Zn(OAc)2·2H2O with the ligand bimb. The X-ray crystal structural analysis indicates that two independent single-stranded helical chains are interwoven like two entwined snakes and held together through hydrogen bonds and π-π interactions.
Co-reporter:Ye Deng, Yue Zhao, Peng Wang, Zhao-Yu Yao, Xiu-Du Zhang, Wei-Yin Sun
Microporous and Mesoporous Materials (15 March 2017) Volume 241() pp:
Publication Date(Web):15 March 2017
DOI:10.1016/j.micromeso.2016.11.027
•MOFs with dicarboxylate and imidazole-containing ligands were obtained.•The frameworks show varied 2D and 3D structures.•Selective adsorption properties of the frameworks were investigated.An exploration of reactions of 1, 3-bis(1-imidazolyl)-5-(imidazol-1-ylmethyl)benzene (biimb) and biphenyl-4, 4′-dicarboxylic acid (H2BPDC) with Co(II) and Mn(II) salts yielded four new coordination polymers [Co(biimb)(BPDC)(H2O)2]·DMA·10H2O (1), [Co(biimb)(BPDC)] (2), [Mn3(biimb)(BPDC)3(H2O)]·2DMF·0.7H2O (3) and [Mn(biimb)2(BPDC)]·2H2O (4) (DMA = N, N-dimethylacetamide, DMF = N, N-dimethylformamide). 1 has pillar-layered 3D structure without interpenetration and can selectively adsorb methyl orange dye molecules, while 2 is an interesting 5-fold interpenetrating 3D framework. 3 is a 3D net with [Mn3(COO)6] sub-units linked by BPDC2− and biimb ligands. Magnetic investigation revealed that there are antiferromagnetic interactions within the trinuclear sub-units in 3. In the case of 4, the coordination of Mn(II) with biimb gives 1D chain, which is further linked by BPDC2− resulting in formation of a 2D network. The structure diversity of 1–4 implies that the varied coordination modes of BPDC2− have remarkable impact in determining the structure and topology of the complexes.
Co-reporter:Zhi-Qiang Liu, Yue Zhao, Peng Wang, Yan-Shang Kang, Mohammad Azam, Saud I. Al-Resayes, Xiao-Hui Liu, Qing-Yi Lu and Wei-Yin Sun
Dalton Transactions 2017 - vol. 46(Issue 28) pp:NaN9029-9029
Publication Date(Web):2017/06/13
DOI:10.1039/C7DT01759F
Herein, two metal–organic frameworks (MOFs), [Co4(μ3-OH)2(L)(BTB)2(H2O)3]·5.6H2O (1) and [Cd3(L)2(BTB)2(μ2-H2O)]·7.4H2O (2), based on 1,3-di(1H-imidazol-4-yl)benzene (L) and 1,3,5-tri(4-carboxyphenyl)benzene (H3BTB), respectively, have been achieved. Compound 1 is a porous three-dimensional (3D) framework with butterfly-like tetranuclear clusters as 7-connected nodes, and compund 2 is a 3D net with a different topology. Remarkably, compounds 1 and 2 exhibit selective adsorption of CO2 over N2 and methyl orange (MO) dye molecules. Magnetic measurements reveal that there are antiferromagnetic interactions within the tetranuclear cluster in 1. Furthermore, 2 was well-dispersed in different solvents, and their luminescent properties were investigated, and the results indicated that 2 could be considered as a potential luminescent probe for the detection of ketone molecules.
Co-reporter:Dan Zhao, Xiao-Hui Liu, Zhuang-Zhi Shi, Chen-Dan Zhu, Yue Zhao, Peng Wang and Wei-Yin Sun
Dalton Transactions 2016 - vol. 45(Issue 36) pp:NaN14190-14190
Publication Date(Web):2016/08/03
DOI:10.1039/C6DT02755E
Developing efficient catalysts for converting carbon dioxide (CO2) into varied organic carbonates is an important scientific goal. By using the NH2-functionalized tripodal ligand 2-((bis(2-aminoethyl)amino)methyl)phenol (HL), three dinuclear metal–organic complexes [Zn(L)]2·2ClO4 (1), [Cu(L)]2·2ClO4·2H2O (2) and [Cd(L)]2·2ClO4 (3) have been successfully isolated and structurally characterized using single-crystal X-ray diffraction analyses. Considering the dinuclear metal centers and the NH2-functional groups in the structures, 1–3 were investigated as catalysts for converting CO2 into organic carbonates, and the results show that 1–3 exhibit an outstanding ability for converting CO2 into varied organic carbonates at atmospheric pressure (0.1 MPa). The catalytic system also displays a wide substrate scope and high catalytic activity, and the reaction mechanism has been proposed herein.
Co-reporter:Shui-Sheng Chen, Min Chen, Satoshi Takamizawa, Man-Sheng Chen, Zhi Su and Wei-Yin Sun
Chemical Communications 2011 - vol. 47(Issue 2) pp:NaN754-754
Publication Date(Web):2010/11/11
DOI:10.1039/C0CC04085A
A highly stable copper(II) microporous framework with cylindrical channels constructed from 1,4-di(1H-imidazol-4-yl)benzene (H2L) and CuCl2·2H2O is composed of Cu(II)-imidazolate tubes interconnected by the 1,4-phenylene group of L2−, and shows temperature dependent selective gas sorption properties.
Co-reporter:Qing Liu, Li-Na Jin and Wei-Yin Sun
Chemical Communications 2012 - vol. 48(Issue 70) pp:NaN8816-8816
Publication Date(Web):2012/07/16
DOI:10.1039/C2CC34192A
A porous coordination polymer [Cu3(btc)2] with controllable size and morphology from nanocube to microoctahedron was readily synthesized in an ethanol–water mixture at room temperature by adjusting the concentration of the surfactant and the polymer shows size- and morphology-dependent sorption properties.
Co-reporter:Gao-Chao Lv, Peng Wang, Qing Liu, Jian Fan, Kai Chen and Wei-Yin Sun
Chemical Communications 2012 - vol. 48(Issue 82) pp:NaN10251-10251
Publication Date(Web):2012/09/12
DOI:10.1039/C2CC35456J
A series of Cu(II) complexes showed unprecedented reversible cascades of single-crystal-to-single-crystal (SCSC) transformations, and more interestingly, very rapid crystal dynamic processes were observed in this system via the substitution of coordinating components without loss of single crystallinity.
Co-reporter:Man-Sheng Chen, Min Chen, Satoshi Takamizawa, Taka-aki Okamura, Jian Fan and Wei-Yin Sun
Chemical Communications 2011 - vol. 47(Issue 13) pp:NaN3789-3789
Publication Date(Web):2011/02/02
DOI:10.1039/C0CC04689B
A unique 4-fold interpenetrated (10,3)-b copper(II) framework exhibits reversible dehydration and rehydration in a single-crystal-to-single-crystal (SC–SC) process, and the dehydrated material can encapsulate CH3OH molecules, again in a SC–SC fashion, and shows selective adsorption of H2 and CO2 over N2.
Co-reporter:Shui-Sheng Chen, Min Chen, Satoshi Takamizawa, Peng Wang, Gao-Chao Lv and Wei-Yin Sun
Chemical Communications 2011 - vol. 47(Issue 17) pp:NaN4904-4904
Publication Date(Web):2011/03/25
DOI:10.1039/C1CC10899A
Two porous supramolecular isomeric frameworks show unique sorption properties, one with temperature dependent stepwise and hysteretic selective sorption of CO2 while the other one shows gas uptake capacity for CO2, N2, H2 and CH4 at low temperature and selective sorption of CO2 over N2 around room temperature.
Co-reporter:Pei-Pei Cui, Xiu-Du Zhang, Yue Zhao, Ai-Yun Fu and Wei-Yin Sun
Dalton Transactions 2016 - vol. 45(Issue 6) pp:NaN2597-2597
Publication Date(Web):2015/12/18
DOI:10.1039/C5DT03091A
Under solvothermal conditions, reactions of pyridine-3,5-bis(phenyl-4-carboxylic acid) (H2L) with lanthanide metal salts give rise to three new metal–organic frameworks (MOFs) with the formula {[Ln4(L)3(μ3-OH)4(H2O)4]·(NO3)2·solvent}n [Ln = Er (1), Yb (2) and Lu (3)]. The complexes were characterized by single crystal and powder X-ray diffraction, IR and thermogravimetric analyses. They have the same two-fold interpenetrating three-dimensional (3D) framework structures with [Ln4(COO)6(μ3-OH)4(H2O)4] clusters as secondary building units (SBUs) and a rare 6-connected lcy topology with the point (Schläfli) symbol of {33·59·63}. Interestingly, 1–3 show selective and hysteretic sorption of CO2 over N2, and the photoluminescence properties of the complexes were also investigated.
Co-reporter:Qing Liu, Ji-Min Yang, Fan Guo, Li-Na Jin and Wei-Yin Sun
Dalton Transactions 2016 - vol. 45(Issue 13) pp:NaN5847-5847
Publication Date(Web):2016/02/23
DOI:10.1039/C5DT04944J
Nano/microscale lanthanide porous coordination polymer MIL-103(Eu) [Eu(BTB)] (H3BTB = 4,4′,4′′-benzene-1,3,5-triyl-tribenzoic acid) crystals have been fabricated at room temperature by a facile, convenient and environmentally friendly method. The structures of the products were confirmed by powder X-ray diffraction, and the crystal morphologies, including microrods, nanorods and nanospheres, were characterized by scanning electron microscopy. It is found that the addition of sodium acetate and the concentration of the reactants have an important impact on the morphology and size of the MIL-103(Eu) crystals. Gas adsorption measurements reveal that the products show high specific surface areas among the rare earth based coordination polymers and the MIL-103(Eu) nanorods can selectively adsorb CO2 over N2 under ambient conditions. Furthermore, all the products exhibit red emission corresponding to the 5D0 → 7F2 transition of the Eu(III) ion, and MIL-103(Eu) nanorods display sensitive and selective sensing for Cu(II) ions and acetone molecules in solution.
Co-reporter:Zhao-Peng Qi, Ji-Min Yang, Yan-Shang Kang, Fan Guo and Wei-Yin Sun
Dalton Transactions 2016 - vol. 45(Issue 21) pp:NaN8759-8759
Publication Date(Web):2016/04/20
DOI:10.1039/C6DT00886K
A facile and universal method was developed to evaluate the relative water stability of porous MOFs and morphological evolution was achieved by controlling the volume ratio of DMF and H2O. The relative water stability of the studied MOFs is in the order HKUST-1 > MOF-505 ∼ UMCM-150 > NOTT-101 > DUT-23(Cu) > [Zn2(BPnDC)2(DABCO)] ∼ [Cu3(TPTrC)2(DABCO)] > MOF-5. In addition, DUT-23(Cu) [Cu6(BTB)4(BPY)3] (H3BTB = 4,4′,4′′-benzene-1,3,5-triyl-tribenzoic acid, BPY = 4,4′-bipyridine) nanoparticles obtained with a volume ratio of DMF and H2O of 18:2 show excellent adsorption capacity for methylene blue (MB) (814 mg g−1) with high selectivity compared with methyl orange, rhodamine B, and acid chrome blue K dyes due to the size and the electrostatic repulsion effects in aqueous solution.
Co-reporter:Yu-Ling Li, Dan Zhao, Yue Zhao, Peng Wang, Huai-Wei Wang and Wei-Yin Sun
Dalton Transactions 2016 - vol. 45(Issue 21) pp:NaN8823-8823
Publication Date(Web):2016/04/20
DOI:10.1039/C6DT00568C
Based on 1,3,5-tris(1-imidazolyl)benzene (tib) and 2,2′-dinitro-4,4′-biphenyldicarboxylic acid (H2dnbpdc), four new metal–organic frameworks [M3(tib)(dnbpdc)3(H2O)2] [M = Mn (1), Cd (2)], [Zn3(tib)2(dnbpdc)2.5(Hdnbpdc)]·4DEF (3), and [Cd(tib)(dnbpdc)(H2O)]·DMF·H2O (4) (DEF = N,N-diethylformamide, DMF = N,N-dimethylformamide) were successfully synthesized. Isomeric 1 and 2 were unusual 8-connected uninodal three-dimensional (3D) frameworks with a point symbol of {33·415·59·6}. Compound 3 was a (3,3,4,4)-connected 4-nodal 3D net with a point symbol of {4·6·8}2{4·62}{4·85}{62·83·10}, whereas 4 was a one-dimensional (1D) chain, which was further linked with neighboring 1D chains by hydrogen bonding interactions to give a 3D framework. It is interesting that 1 displayed ferromagnetic and antiferromagnetic interactions within the trinuclear Mn(II) subunit. We also performed Knoevenagel condensation reactions catalyzed by activated 3 to demonstrate its heterogeneous catalytic property. Furthermore, the adsorption property of 3 was also investigated.
Co-reporter:Shui-Sheng Chen, Peng Wang, Satoshi Takamizawa, Taka-aki Okamura, Min Chen and Wei-Yin Sun
Dalton Transactions 2014 - vol. 43(Issue 16) pp:NaN6020-6020
Publication Date(Web):2014/01/09
DOI:10.1039/C3DT53388C
The use of a 4-imidazole containing tripodal ligand 1,3,5-tri(1H-imidazol-4-yl)benzene (H3L) enabled isolation of two three-dimensional (3D) porous metal–organic frameworks (MOFs) [Zn(HL)]·solvent (1) and [Cd(H3L)2](ClO4)2·10.5H2O (2) featuring 4,4- and 3,6-connected nets related to the structures of ecl and pyrite, respectively. Framework 1 has 3D channels based on Zn–Im− (Im− = imidazolate) moieties due to partial deprotonation of the 1H-imidazol-4-yl groups of H3L while porous framework 2 is constructed by the coordination of neutral H3L ligands with Cd(II). Desolvated solid 1′ showed remarkable uptake for CO2, N2, H2, CH4 gases as well as the volatile organic vapor of MeOH, EtOH, i-PrOH and C6H6, significantly, exhibiting temperature dependent selective gas sorption for CO2 over N2. Grand Canonical Monte Carlo (GCMC) simulations were performed to elucidate the mechanism of the selective gas adsorption. Cage-like motifs are found in pyrite-net 2, in which ClO4− anions are hosted, and the results of IR, elemental analysis and PXRD measurements confirm that 2 has a reversible anion exchange property among perchlorate, nitrate and nitrite anions.
Co-reporter:Ji-Min Yang, Qing Liu, Yan-Shang Kang and Wei-Yin Sun
Dalton Transactions 2014 - vol. 43(Issue 44) pp:NaN16712-16712
Publication Date(Web):2014/09/23
DOI:10.1039/C4DT02429J
IRMOF-3 nano/microcrystals with controllable morphologies and sizes were successfully obtained by a simple solvothermal method. The shape evolution of IRMOF-3 crystals from cube to truncated cube, cuboctahedron, truncated octahedron and finally to octahedron was achieved by adjusting the amount of surfactant. The surfaces of the IRMOF-3 nano/microstructures are affected by the reaction temperature, and the nano/microparticles show shape-dependent sorption properties.
Co-reporter:Ji-Ai Hua, Yue Zhao, Yan-Shang Kang, Yi Lu and Wei-Yin Sun
Dalton Transactions 2015 - vol. 44(Issue 25) pp:NaN11532-11532
Publication Date(Web):2015/05/13
DOI:10.1039/C5DT01386K
Starting from the same metal salts and mixed organic ligands of 1,3,5-tris(1-imidazolyl)benzene (tib) and 2-bromo-1,4-benzenedicarboxylic acid (H2BDC-Br), two novel zinc(II) coordination polymers [Zn2(tib)2(BDC-Br)]2·2SO4·17H2O (1) and [Zn4(tib)2(BDC-Br)3(H2O)4SO4]·7.5H2O·2.5DMF (2) (DMF = N,N-dimethylformamide) were obtained by using different solvent systems of DMF/H2O and DMF/EtOH/H2O, respectively. 1 is an unusual (3,4)-connected 3D net with a Point symbol of {4·8·104}{4·8·10}, while 2 is a complicated 1D chain, which is further connected to form a 3D supramolecular architecture by hydrogen bonding interactions. In particular, 1 and 2 exhibit selective adsorption of CO2 over N2 and show good selectivity for detection of acetone via fluorescence quenching.
Co-reporter:Zhao-Peng Qi, Ji-Min Yang, Yan-Shang Kang and Wei-Yin Sun
Dalton Transactions 2015 - vol. 44(Issue 38) pp:NaN16893-16893
Publication Date(Web):2015/08/24
DOI:10.1039/C5DT02636A
A facile and controllable synthesis of porous framework [Cu3(L)2(DABCO)] (1) (H3L = 1,1′:3,1′′-terphenyl]-4,4′′,5′-tricarboxylic acid; DABCO = 1,4-diazabicyclo[2.2.2]octane) microcrystals was realized with morphology evolution from a tetragonal plate to an elongated tetragonal bipyramid, and the particle size changes by tuning the volume ratio of mixed solvents of DMF and H2O. Interestingly, the exposed high-energy {103} crystal facet can be easily tuned by controlling the supersaturation through the increase of the solution concentration, resulting in the formation of spindle microcrystals. It was found that both H2O and HCl play important roles in the morphology evolution process. The gas adsorption properties were found to be dependent on the morphology of microcrystals, and the elongated tetragonal bipyramidal microcrystals show the largest BET surface area.
Co-reporter:Yue Zhao, Kai Chen, Jian Fan, Taka-aki Okamura, Yi Lu, Li Luo and Wei-Yin Sun
Dalton Transactions 2014 - vol. 43(Issue 5) pp:NaN2258-2258
Publication Date(Web):2013/10/25
DOI:10.1039/C3DT52655K
A family of silver(I) complexes, [Ag2(L)2(OOCCF3)2] (1), [Ag(L)0.5(OOCCF3)] (2), [Ag(L)2](OOCCF3)(H2O)2 (3), was obtained by reactions of 4,4′-di(2-oxazolinyl)biphenyl (L) and AgOOCCF3 in different reaction media. Compound 1 has a 1D chain structure with alternative connections between the Ag(I) and L ligand. When the crystal nucleation inductor, pyrazine, was added into the reaction system, complex 2 was isolated with no pyrazine observed in its structure. In 2, the 1D inorganic chains formed by Ag(I) cations and OOCCF3− anions were connected by the L ligand to produce a 2D network. When a different inductor, imidazole, was added into the reaction system, 3 with (4,4) topology was synthesized, and again no imidazole was found in 3. When 1–3 were used as catalysts for cycloaddition reactions between imino esters and methyl acrylate, 3 affords the highest yield, in which the particular size of the channels in 3 led to its selective catalytic performance.
Co-reporter:Yue Zhao, Xin Zhou, Taka-aki Okamura, Min Chen, Yi Lu, Wei-Yin Sun and Jin-Quan Yu
Dalton Transactions 2012 - vol. 41(Issue 19) pp:NaN5896-5896
Publication Date(Web):2012/03/08
DOI:10.1039/C2DT30134B
A novel supramolecular complex [Ag(L)(NO3)] (1) was synthesized by reaction of the oxazoline-containing ligand 1,4-bis(4,5-dihydro-2-oxazolyl)benzene (L) with silver(I) nitrate and its structure was determined by single-crystal X-ray diffraction. Structurally speaking, the one-dimensional (1D) zigzag chains of 1, in which the Ag(I) is three-coordinated with distorted trigonal-planar coordination geometry, are linked together by the hydrogen bonding interactions to form a three-dimensional (3D) supramolecular structure. It was found that the silver supramolecule 1 catalyzes the three-component coupling reactions of aldehyde, alkyne, and amine in the air at room temperature to generate propargylic amines with high efficiency. No additional co-catalyst or activator is required. A variety of aldehydes and amines were used to demonstrate the versatility of the reaction.
Co-reporter:Zheng-Shuai Bai, Jing Xu, Taka-aki Okamura, Man-Sheng Chen, Wei-Yin Sun and Norikazu Ueyama
Dalton Transactions 2009(Issue 14) pp:NaN2539-2539
Publication Date(Web):2009/02/12
DOI:10.1039/B816205K
Six novel three-dimensional (3D) dense organic–lanthanide(III) frameworks with formula {[Ln(HBPTCA)(H2O)]·3H2O}n [Ln = La (1), Ce (2), Sm (3)] and [Ln4(BPTCA)3(H2O)4]n [Ln = Tb (4), Dy (5), Ho (6)] were obtained by reactions of the corresponding lanthanide nitrate salt with 4,4′-bipyridine-2,2′,6,6′-tetracarboxylic acid (H4BPTCA) under different conditions. Complexes 1–3 have the same structure with (4, 62)2(42, 610, 83) topology, which is rare binodal (3, 6)-connecting rutile structure, while the complexes 4–6 also with the same structure have different topology of (42, 6)4(6, 82)4(43, 63)4(42, 64)6(44, 65, 85, 10). The results indicate that the reaction conditions have great influence on the structure of the resulted complexes in this system. In addition, the H4BPTCA was found to be an effective bridging ligand for construction of novel lanthanide-based dense hybrids, and two new coordination modes of the BPTCA4− were found in the complexes. The photoluminescent property of 4 and magnetic properties of 2, 5 and 6 were also investigated.
Co-reporter:Yong-Qing Huang, Zhong-Liang Shen, Taka-aki Okamura, Yan Wang, Xiao-Feng Wang, Wei-Yin Sun, Jin-Quan Yu and Norikazu Ueyama
Dalton Transactions 2008(Issue 2) pp:NaN213-213
Publication Date(Web):2007/12/04
DOI:10.1039/B714502K
Seven new silver(I) complexes of the formula [Ag2(L)2(CF3SO3)2] (1), [Ag2(L)2(CH3SO3)2] (2) [Ag2(L)2](BF4)2 (3), [Ag3(L)2(NO3)2]NO3·5H2O (4), [Ag2(L)(NO3)2]·CH3OH (5), [Ag2(L)2](ClO4)2 (6) and [Ag3(L)2(CH3CN)3](ClO4)3 (7) have been synthesized by reactions of 1,3,5-tris(2-oxazolinyl)benzene (L) with varied silver(I) salts under different conditions. The influences of counter anions and reaction conditions on the structure of the complexes are discussed. Three complexes 1, 2 and 3 with two kinds of different 1D chain structures were obtained under the same synthetic conditions by using different silver(I) salts, and the ligand L was found to adopt bis-monodentate (1 and 2) and tris-monodentate (3) coordination modes respectively. On the other hand, by using the same silver(I) nitrate or silver(I) perchlorate but different reaction solvents, 4 and 5 or 6 and 7 were isolated respectively. Complexes 4 and 5 have different 1D chain structures, and 6 is isostructural with 3. However, 7 is a tri-nuclear, propeller-shaped M3L2 supramolecular capsule in which L adopts a cis,cis,cis-conformation, while the ligand L in 3–6 has cis,trans,trans-conformation. The results revealed that the nature of the counter anions, such as their size, coordination ability and coordination mode, and the reaction conditions all have great impact on the structure of the complexes. The complexes were also characterized by electrospray mass spectrometry. Furthermore, complex 7 exhibited modest second-harmonic-generation (SHG) efficiency.
Co-reporter:Qian Chu, Guang-Xiang Liu, Yong-Qing Huang, Xiao-Feng Wang and Wei-Yin Sun
Dalton Transactions 2007(Issue 38) pp:NaN4311-4311
Publication Date(Web):2007/08/08
DOI:10.1039/B707159K
Five novel coordination polymers [Zn2(OA)(4,4′-bipy)(H2O)]·0.5(4,4′-bipy) (1), [Zn2(OA)(dib)(H2O)]·H2O (2), [Zn2(OA)(bbi)2]·3H2O (3), [Zn2(OA)(phen)2(H2O)] (4) and [Zn4(OA)2(2,2′-bipy)2(H2O)]·2H2O (5) were obtained by hydrothermal reactions of Zn(NO3)2·6H2O with a V-shaped multicarboxylate ligand 3,3′,4,4′-oxydiphthalic acid (H4OA) and a series of N-donor ligands, namely 4,4′-bipyridine (4,4′-bipy), 1,4-di(1-imidazolyl)benzene (dib), 1,1′-(1,4-butanediyl)bis(imidazole) (bbi), 1,10-phenanthroline (phen), 2,2′-bipyridine (2,2′-bipy). The structures of the complexes were established by single-crystal X-ray diffraction analysis. Complex 1 exhibits a robust 3D porous structure with uncoordinated 4,4′-bipy molecules filling the cavities. Complexes 2 and 5 show a complicated 3D framework, while complexes 3 and 4 have a 2D network and a 1D helical chain structure, respectively. The results indicate that the multicarboxylate OA4− ligand can adopt varied coordination modes in the formation of the complexes and the influence of the N-donor ligand on the structure of the complexes is discussed. The photoluminescence properties of H4OA and 1–5 were studied in the solid state at room temperature. Moreover, nonlinear optical measurements showed that 5 displayed a second-harmonic-generation (SHG) response of 0.5 times of that for urea. The results suggested that the configuration and flexibility of the ligands play a key role in directing the related properties of the complexes.
Co-reporter:Dan Zhao, Xiao-Hui Liu, Yue Zhao, Peng Wang, Yi Liu, Mohammad Azam, Saud I. Al-Resayes, Yi Lu and Wei-Yin Sun
Journal of Materials Chemistry A 2017 - vol. 5(Issue 30) pp:NaN15807-15807
Publication Date(Web):2017/07/03
DOI:10.1039/C7TA03849F
Excess and deficiency of iron(III) and antibiotics from normal permissible limits will induce serious disorders, so their detection is important but challenging. In this work, by introducing a new amino triazole ligand N1-(4-(1H-1,2,4-triazole-1-yl)benzyl)-N1-(2-aminoethyl)ethane-1,2-diamine (L), a series of Cd(II)-based metal–organic frameworks (MOFs) [Cd3(BDC)3(DMF)2] (1), [Cd(L)(BDC)]2·2DMF·H2O (2), [NaCd2(L)(BDC)2.5]·9H2O (3), [Cd2(L)(2,6-NDC)2]·DMF·5H2O (4) and [Cd2(L)(BPDC)2]·DMF·9H2O (5) were synthesized. MOFs 1, 2 and 3 obtained under the same conditions with the same auxiliary ligand (H2BDC) but different amounts of alkali (NaOH) show distinct 3D, 1D and 3D framework structures, respectively, in which L and BDC2− exhibit varied coordination modes. 4 and 5 with 3D structures were isolated by using longer auxiliary ligands of 2,6-H2NDC and H2BPDC. The porosity and excellent fluorescence performance of 3, 4 and 5 make them potential luminescent sensors for Fe(III) and antibiotics. The results show that 3, 4 and 5 represent high sensitivity for the detection of Fe(III) ions with detection limits of 155 ppb for 3, 209 ppb for 4 and 297 ppb for 5 due to the existence of open channels and chelating NH2 sites. In addition, the strong emissions of 3, 4 and 5 can be quenched efficiently by trace amounts of NFs (nitrofurazone, NZF; nitrofurantoin, NFT; furazolidone, FZD) antibiotics even in the presence of other competing antibiotics such as β-lactams (penicillin, PCL). They are responsive to NZF with detection limits of 162 ppb for 3, 75 ppb for 4 and 60 ppb for 5.
![[1,1':3',1''-Terphenyl]-2'-thiol, 5'-phenyl-](http://img.cochemist.com/ccimg/4500/4435-66-9.png)
![[1,1':3',1''-Terphenyl]-2'-thiol, 5'-phenyl-](http://img.cochemist.com/ccimg/4500/4435-66-9_b.png)