Chao Qin

A noncovalently connected metal–organic framework assembled from a Ni(III)-supported polyoxometalate–imidazolate hybrid

Co-reporter:Yan-Qing Jiao;Meng-Ting Li;Zhong-Min Su

CrystEngComm (1999-Present) 2017 vol. 19(Issue 13) pp:1721-1724

Publication Date(Web):2017/03/27

DOI:10.1039/C6CE02420C

The first mixed-valence nickel-supported polyoxometalate-based metal–organic framework, (H2mim)[NiIII(Hmim)4][SiW11NiIIO37(OH)2(Hmim)]·3H2O (1) (Hmim = 2-methylimidazole), has been synthesized using a steam-assisted conversion method, and is constructed from noncovalent interactions (hydrogen bonds and π⋯π stacking interactions). 1 has a repeating honeycomb-shaped internal structure with one-dimensional channels along the direction of the c axis, where the diameter of the aperture is as large as 18.83 Å. Furthermore, the stability and the optical band gaps are investigated.

Two nanoscale Nb containing polyoxometalates based on {P2W15Nb3O62} clusters and chromium cations

Co-reporter:Peng Huang;Xin-Long Wang;De-Qing He;Hai-Yang Wu;Meng Du;Chao Lai;Zhong-Min Su

Dalton Transactions 2017 vol. 46(Issue 39) pp:13345-13348

Publication Date(Web):2017/10/10

DOI:10.1039/C7DT02737K

Two novel mixed-addenda Nb/W polyoxometalates are successfully fabricated, and investigated as anode materials for lithium-ion batteries. For the Cs5K4{Cr3(H2O)12[P2W15Nb3O62]2}·60H2O sample, a reversible capacity (466.6 mA h g−1) and stable cycle performance are obtained.

An unprecedented 3D architecture based on a Nb/W mixed-addendum polyoxometalate and lanthanide–organic complex: synthesis, crystal structure and properties

Co-reporter:Mei-Si Yang;Wei-Chao Chen;Wei Yao;Ying-Xue Yin;Zhong-Min Su

New Journal of Chemistry (1998-Present) 2017 vol. 41(Issue 19) pp:10532-10536

Publication Date(Web):2017/09/25

DOI:10.1039/C7NJ02011B

For the first time, an unprecedented 3D framework based on lanthanide-containing Nb/W mixed-addendum polyoxometalate [H3La8(H2O)32(C6H5NO2)6][SiW9Nb3O40]3·8H2O (1) has been obtained by utilizing the steam-assisted conversion method. Meanwhile, the stability, electrochemical behavior, and photoluminescence properties of 1 have also been discussed.

Self-assembly and photocatalytic H2 evolution activity of two nanoscale polytantalotungstates based on unprecedented {Cr3Ta6} and {Cr4Ta12} clusters

Co-reporter:Peng Huang;Xiao-Jun Wang;Jiao-Jiao Qi;Xin-Long Wang;Min Huang;Hai-Yang Wu;Zhong-Min Su

Journal of Materials Chemistry A 2017 vol. 5(Issue 44) pp:22970-22974

Publication Date(Web):2017/11/14

DOI:10.1039/C7TA06822K

Two nanoscale polytantalotungstates (POTTs), Cs5K4{Cr3[Ta3P2W15O62]2(H2O)12}·15H2O (1) and Cs8.5K8Na2H5.5{Cr4[Ta3P2W15O62]4(H2O)12}·53H2O (2), based on unprecedented {Cr3Ta6} and {Cr4Ta12} clusters, respectively, were hydrothermally synthesized. A photocatalytic study revealed that 1 and 2 exhibit significant photocatalytic water splitting activities.

A novel Ta/W mixed-addendum polyoxometalate with photocatalytic properties

Co-reporter:Peng Huang;Hai-Yang Wu;Min Huang;Meng Du;Xin-Long Wang;Zhong-Min Su

Dalton Transactions 2017 vol. 46(Issue 31) pp:10177-10180

Publication Date(Web):2017/08/08

DOI:10.1039/C7DT01890H

An unprecedented polytantalotungstate (POTT), Cs12.5K4.5H[Ta12Si4W37O158]·25H2O (1), based on the {SiW9Ta3O40}7− cluster was hydrothermally synthesized. A photocatalytic study revealed that 1 exhibits significant photocatalytic water splitting activity.

A fluorescent sensor for highly selective sensing of nitro explosives and Hg(II) ions based on a 3D porous layer metal–organic framework

Co-reporter:Liu Yang, Xiao Li, Chao Qin, Kui-Zhan Shao and Zhong-Min Su

CrystEngComm 2016 vol. 18(Issue 25) pp:4765-4771

Publication Date(Web):25 Apr 2016

DOI:10.1039/C6CE00745G

A 3D porous layer metal–organic framework, namely [Cd(BPDC)0.5(L1)(NO3)]·3.4DMF (1), was synthesized under solvothermal conditions. The structure was characterized by single crystal X-ray diffraction analysis, powder X-ray diffraction (PXRD) analysis, thermogravimetric analysis (TGA), infrared spectrophotometry analysis and elemental analysis. The structure of 1 displays a 3D porous layer and can be classified as a (3,4)-connected topology with a point symbol of (42·6·38)2(42·6). The framework is stable to a certain degree. 1 can also be applied as a fluorescent sensor for small-molecule sensing, such as nitrobenzene (NB) and 2,4,6-trinitrophenol (TNP). In addition, 1 is a rare example of MOF-based fluorescent probes targeting environmentally relevant guest species, such as Hg(II) ions in aqueous solution, with high selectivity and sensitivity.

A stable luminescent anionic porous metal–organic framework for moderate adsorption of CO2 and selective detection of nitro explosives

Co-reporter:En-Long Zhou, Peng Huang, Chao Qin, Kui-Zhan Shao and Zhong-Min Su

Journal of Materials Chemistry A 2015 vol. 3(Issue 14) pp:7224-7228

Publication Date(Web):02 Mar 2015

DOI:10.1039/C5TA00231A

A stable luminescent anionic metal–organic framework with unprecedented topological structure was constructed, which showed a certain degree of framework stability in water and acid/base solutions. Furthermore, the compound showed moderate CO2 adsorption and extremely selective detection of 2,4,6-trinitrophenol (TNP) in both an organic solvent and aqueous solution.

A luminescent dye@MOF as a dual-emitting platform for sensing explosives

Co-reporter:Xiao-Li Hu, Chao Qin, Xin-Long Wang, Kui-Zhan Shao and Zhong-Min Su

Chemical Communications 2015 vol. 51(Issue 99) pp:17521-17524

Publication Date(Web):23 Sep 2015

DOI:10.1039/C5CC07004J

An anionic metal–organic framework (MOF) with 1D nanotube channels has been constructed. The charge and size dependent ion-exchange of cationic dyes was investigated. Rho@1 could be used as a dual-emitting fluorescent sensor for sensing explosives by self-referencing energy transfer behaviors.

Syntheses, structures, magnetic and luminescence properties of a series of coordination polymers constructed from 1,4-naphthalenedicarboxylate and N-donor ligands

Co-reporter:Liu Yang, Chao Qin, Bai-Qiao Song, Xiao Li, Chun-Gang Wang and Zhong-Min Su

CrystEngComm 2015 vol. 17(Issue 24) pp:4517-4524

Publication Date(Web):07 May 2015

DOI:10.1039/C5CE00539F

Five new coordination polymers constructed from 1,4-naphthalenedicarboxylate and N-donor ligands including [Cd2(1,4-ndc)2(bpy)2]·0.5H2O (1), [Cd(1,4-ndc)(phen)]·0.5H2O (2), [Cu2(1,4-ndc)2(L1)]·H2O (3), [Co3(H2O)2(1,4-ndc)4(HL2)2] (4), and [Cd2(NO3)2(1,4-ndc)(L3)2]·H2O (5) have been synthesized under hydrothermal conditions and characterized by elemental analysis, infrared spectroscopy, powder X-ray diffraction and single crystal X-ray diffraction. Compounds 1 and 2 are 2D layers with 4-connected (44·62) topology. Compound 3 is a 3D two-fold interpenetrating pcu network based on a binuclear cluster. Compound 4 exhibits an eight-connected bcu network constructed by a trinuclear cluster. Compound 5 is a 3D two-fold interpenetrating network with uninodal 4-connected cds (CdSO4) topology. Furthermore, the magnetic properties of compounds 3 and 4 were investigated and the photoluminescence properties of compounds 1, 2 and 5 show that the three compounds have strong emission under λex = 320 nm at room temperature.

Pillared metal organic frameworks for the luminescence sensing of small molecules and metal ions in aqueous solutions

Co-reporter:Fu-Hong Liu, Chao Qin, Yan Ding, Han Wu, Kui-Zhan Shao and Zhong-Min Su

Dalton Transactions 2015 vol. 44(Issue 4) pp:1754-1760

Publication Date(Web):17 Nov 2014

DOI:10.1039/C4DT02961E

Two novel pillared MOFs (metal organic frameworks) [Zn2(trz)2(tda)]·DMA CH3OH (1) and [Zn2(trz)2(bpdc)]·DMA (2) were obtained under solvothermal conditions. The resulting MOFs show similar structures but with different interlayer distances based on the different carboxylate ligands. 1 and 2 display a certain degree of framework stability in both acid/base solutions and water. The luminescence intensities of the activated phases 1a and 2a are sensitive to metal ions, particularly Fe3+ and Cd2+ ions. Furthermore, the luminescent properties of 1a and 2a well dispersed in different solvents have also been investigated systematically, which demonstrate distinct solvent-dependent luminescent spectra with emission intensities that are significantly quenched by acetone, nitrobenzene and trinitrotoluene.

Assembly of organic–inorganic hybrid materials constructed from polyoxometalate and metal–1,2,4-triazole units: synthesis, structures, magnetic, electrochemical and photocatalytic properties

Co-reporter:Yan-Qing Jiao, Chao Qin, Hong-Ying Zang, Wei-Chao Chen, Chun-Gang Wang, Tian-Tian Zheng, Kui-Zhan Shao and Zhong-Min Su

CrystEngComm 2015 vol. 17(Issue 10) pp:2176-2189

Publication Date(Web):14 Jan 2015

DOI:10.1039/C4CE02007C

A series of organic–inorganic hybrid compounds built from Keggin and Wells–Dawson polyoxometalates and TM-trz complexes (Htrz = 1,2,4-triazole) were obtained at different pH values under hydrothermal conditions, namely, [Co2(H2O)2(Htrz)5][SiW12O40]·2.5H2O (1), [Zn5(Htrz)8(trz)2(H2O)8][SiW12O40]2·10H2O (2), [CuI2CuII4(Htrz)4(trz)4Cl2][GeW12O40]·15H2O (3), [CuI2CuII4(Htrz)4(trz)4Cl2][SiW12O40]·15H2O (4), K2Na2(H2O)2[Co11(trz)14(H2O)14][P2W18O62]2·29H2O (5) and [Cu12(trz)10(Htrz)2(OH)4(SO4)2(H2O)6][P2W18O62]·28H2O (6). All of the compounds were characterized using single-crystal X-ray diffraction, TG analysis and powder X-ray diffraction. Compound 1 contains a kind of bimetallic–organic segment [Co2(Htrz)5]4+, which could be regarded as a quasi-sinusoid-like chain. 2 is a dimer constructed from two [SiW12O40]4− units linked by a [Zn5(trz)2(Htrz)8]8+ motif. In 3 and 4, the 2D wall-like layers constructed by the Cu(II) ions and Htrz ligands are extended into 3D frameworks by polyanions. 5 shows a complicated three-dimensional (3D) framework with a {412·612·84}{46}2 topology. Compound 6 is also a complicated 3D structure based on a triangular trinuclear Cu-trz unit and [P2W18O62] polyanions. To the best of our knowledge, 6 represents the largest copper cluster linked by amines in a POM system. Structural diversities reveal that the pH value of the reaction system plays a crucial role in the assembly of POM-based hybrids. Moreover, the optical band gaps, electrochemical properties, magnetic properties and the photocatalytic properties of the compounds have been investigated.

Spontaneous chiral resolution of a rare 3D self-penetration coordination polymer for sensitive aqueous-phase detection of picric acid

Co-reporter:Bai-Qiao Song, Chao Qin, Yu-Teng Zhang, Xue-Song Wu, Liu Yang, Kui-Zhan Shao and Zhong-Min Su

Dalton Transactions 2015 vol. 44(Issue 42) pp:18386-18394

Publication Date(Web):09 Sep 2015

DOI:10.1039/C5DT03218K

Two unprecedented homochiral enantiomers based on two different kinds of rigid ligands, namely [Cd(NDC)L]2·H2O (1R and 1L), have been synthesized under hydrothermal conditions through spontaneous resolution. Their structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR, and thermogravimetric (TG) analysis. The resulting framework 1, constructed by four kinds of homo-handed helical chains represents the first 3D self-penetrating framework formed by decoration of single (10,3)-a net with helical chains. The single (10,3)-a net in 1 formed by three kinds of different homo-handed helical chains is different from the standard one, which should be ascribed to the usage of V-shaped ligand L. A unique self-penetration motif can be discovered in 1 where one helical chain alternately passes through 10-membered shortest circuits linked to each other and in contrary, the corresponding circuits are bound to the helical chain. Interestingly, 1 exhibits fluorescent emission in both the solid and solution phase. The uncoordinated nitrogen atom and amino group from the triazole core on the crystal surface make it suitable to detect picric acid in water. The luminescence intensity of 1 in water can be efficiently quenched by the addition of picric acid (PA). The sensitive detection of PA can be continuously performed for at least five cycles without diminishing the fluorescence intensity and destroying the framework structure of 1. The possible quenching mechanisms for PA are also investigated.

A 2D bilayered metal–organic framework as a fluorescent sensor for highly selective sensing of nitro explosives

Co-reporter:Xiao-Li Hu, Fu-Hong Liu, Chao Qin, Kui-Zhan Shao and Zhong-Min Su

Dalton Transactions 2015 vol. 44(Issue 17) pp:7822-7827

Publication Date(Web):19 Mar 2015

DOI:10.1039/C5DT00515A

A novel Cd-MOF (metal organic framework) [Cd3(NTB)2(DMA)3]·2DMA (H3NTB = 4,4′,4′′-nitrilotrisbenzoic acid; DMA = N,N-dimethylacetamide) (1) was obtained under solvothermal conditions. The resulting MOF exhibits a novel (2D→3D) interdigitated architecture that is obtained from a bilayered motif with hexagonal grids. Luminescence properties of the activated phase of 1a well dispersed in different solvents have also been investigated systematically, which demonstrate distinct solvent-dependent luminescence spectra with emission intensities significantly quenched toward nitrobenzene (NB) and 2,4,6-trinitrophenol (TNP). The results reveal that 1 can be applied as a fluorescent sensor for the detection of TNP with high sensitivity, selectivity, and recyclability.

Coordination assemblies of seven metal-organic frameworks based on a bent connector: structural diversity and properties

Co-reporter:Bai-Qiao Song, Chao Qin, Yu-Teng Zhang, Xue-Song Wu, Hong-Sheng Liu, Kui-Zhan Shao and Zhong-Min Su

CrystEngComm 2015 vol. 17(Issue 16) pp:3129-3138

Publication Date(Web):11 Mar 2015

DOI:10.1039/C4CE02473G

Seven new coordination polymers, namely, [Zn(L)(bdc)]·2H2O (1), [Zn(L)(2-NH2-bdc)]·2H2O (2), [Zn(L)(bdc)]·1.75DMF·0.5H2O (3), [Zn(L)(oba)]·H2O (4), [Co(L)(oba)]·H2O (5), [Cd2(L)2(bdc)(NO3)2]·2DMF (6) and [Cd(L)(ndc)(H2O)] (7) (L = 4-amino-3,5-bis(4-imidazol-1-ylphenyl)-1,2,4-triazole, H2bdc = 1,4-benzenedicarboxylic acid, 2-NH2-H2bdc = 2-amino-1,4-benzenedicarboxylic acid, H2oba = 4,4′-oxydibenzoic acid and H2ndc = 1,4-naphthalenedicarboxylic acid), have been synthesized. The structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR, and thermogravimetric (TG) analysis. 1 and 2 feature a similar three-fold interpenetrating network combined with interdigitation which extends the structure into a three-dimensional framework. 3 is a two-fold interpenetrating framework showing intralayer porosity and interdigitation. Compounds 1 and 3 represent a pair of supramolecular isomers where structural motifs and different interpenetration modes exist; compounds 4 and 5 are isostructural and display the same three-fold interpenetrating framework where two types of interlaced triple-stranded helices A and B can be found. The triple-stranded helices with opposite chirality for each type are distributed in adjacent layers. Compound 6 exhibiting a unique simultaneous threading fashion of adjacent polymeric motifs gives the novel (2D → 3D) polythreaded array where coordinated NO3− anions act as the dangling ligands. Compound 7 is a 6-connected 3D self-penetrating network where right- and left-handed single-stranded helical chains (AR and AL) and interlaced triple-stranded helices (BR and BL) coexist. The luminescence properties of compounds 1–7 were also measured and discussed.

A novel [4 + 3] interpenetrated net containing 7-fold interlocking pseudo-helical chains and exceptional catenane-like motifs

Co-reporter:Bai-Qiao Song, Chao Qin, Yu-Teng Zhang, Li-Tao An, Kui-Zhan Shao and Zhong-Min Su

Dalton Transactions 2015 vol. 44(Issue 6) pp:2844-2851

Publication Date(Web):22 Oct 2014

DOI:10.1039/C4DT02808B

A novel interpenetrating metal–organic framework, namely [Zn3L2(oba)3(H2O)2]·4H2O (1), has been synthesized under hydrothermal conditions. Its structure was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR, and thermogravimetric (TG) analysis. In the structure of 1, the rigid and flexible V-shaped ligands link Zn(II) to form a 3D structure where two types of helices and four types of pseudo-helical chains containing three pairs of enantiomers and two pairs of conformational isomers have been characterized. One such 3D framework incorporates six identical networks to form a 7-fold interpenetrated 3D framework. From the topological analysis, the Zn(II) ions act as three- and four-connected nodes, and oba as well as L are linkers. The framework of compound 1 can be classified as a new (63)2(65·8) topology, which is a novel (3,3,4)-connected [4 + 3] 7-fold interpenetrating net showing 7-fold interlocking pseudo-helical chains and a unique catenane-like motif with Hopf links. In addition, the luminescence properties of the compound are discussed.

Assembly of Zn-metal organic frameworks based on a N-rich ligand: selective sorption for CO2 and luminescence sensing of nitro explosives

Co-reporter:Xiao-Li Hu, Chao Qin, Liang Zhao, Fu-Hong Liu, Kui-Zhan Shao and Zhong-Min Su

RSC Advances 2015 vol. 5(Issue 61) pp:49606-49613

Publication Date(Web):22 May 2015

DOI:10.1039/C5RA05945C

Two novel Zn(II) coordination polymer compounds, namely, [Zn3(HL)2(fma)2]·DMA·H2O (1) and [Zn2(μ3-OH)(HL)(Br-bdc)]·0.5DMA·CH3OH·H2O (2) have been successfully obtained with 1-(5-tetrazolyl)-4-(1-imidazolyl) benzene ligand and dicarboxylic acids (fma = fumaric acid; Br-bdc = 2-bromoterephthalic acid). Compound 1 exhibits a 3D framework with a square aperture diameter for the channel is 8.8 × 8.8 Å2, and the framework can be simplified as a (3,4)-connected tfj network with the point symbol of {4.82}4{42.84}2{84.122} topology. In compound 2, the HL ligand forms a 2D sheet of Zn(HL) by linking Zn ions along the c axis, which are further connected by double Br-bdc pillars resulting in unique bi-pillared-layer type 3D frameworks. The result, 1a, exhibits a certain degree of CO2 uptake and selective CO2/N2 adsorption capacity. Furthermore, luminescent properties of 1a well dispersed in different solvents have also been investigated systematically, which demonstrate distinct solvent-dependent luminescent spectra with emission intensities significantly quenched toward acetone and nitrobenzene.

Cluster-based metal–organic frameworks as sensitive and selective luminescent probes for sensing nitro explosives

Co-reporter:Xiao-Li Hu, Chao Qin, Xin-Long Wang, Kui-Zhan Shao and Zhong-Min Su

New Journal of Chemistry 2015 vol. 39(Issue 10) pp:7858-7862

Publication Date(Web):20 Jul 2015

DOI:10.1039/C5NJ01237F

One new cluster-based metal–organic framework, namely, [Cd2.5Na(NTB)2(DMF)4]·3DMF (1) (NTB = 4,4′,4′′-nitrilotrisbenzoic acid; DMF = N,N-dimethylformamide) has been successfully obtained by employing a C3 symmetric ligand. In 1, the NTB links two different metal centers (single metal and Cd3 cluster) to form two kinds of 1D chains, which linked through the carboxylate O atom of the NTB ligand to give rise to a 3D framework. Moreover, desolved 1 can be well dispersed in different solvents, which demonstrate distinct solvent-dependent luminescence spectra with emission intensities significantly quenched toward nitrobenzene (NB) and 2,4,6-trinitrophenol (TNP). The results reveal that 1 could be applied as a fluorescence sensor for TNP with high sensitivity and selectivity.

POM-based inorganic–organic hybrid compounds: synthesis, structures, highly-connected topologies and photodegradation of organic dyes

Co-reporter:Xiao Li, Liu Yang, Chao Qin, Fu-Hong Liu, Liang Zhao, Kui-Zhan Shao and Zhong-Min Su

RSC Advances 2015 vol. 5(Issue 73) pp:59093-59098

Publication Date(Web):17 Jun 2015

DOI:10.1039/C5RA09339B

Four new polyoxovanadate-based organic–inorganic hybrid materials [MnV2(bpp)2O6] (1), [Ag4V4(bpp)4O12]·2H2O (2) and [M3V6(bpp)4O18·4H2O]·2H2O [M = Ni (3), Zn (4), bpp = 1,3-bis(4-pyridyl)propane] have been synthesized under hydrothermal conditions through the self-assembly of transition metal salts, bpp ligands and ammonium metavanadate. Single-crystal X-ray diffraction analyses show that 1 possesses a three-dimensional framework, constructed from arrays of {V4O12} rings covalently linked through metal–organic units, {Mn(C13H4N2)2}. Compound 2 is an eight-connected self-catenated metal–organic framework, based on bimetallic {Ag4V4O12} clusters as nodes. Compounds 3 and 4 are isostructural, both of them exhibit an intriguing 6,10-connected network. The structure of 4, as an example, is based on single zinc atoms as six-connected nodes, as well as bimetallic {Zn2V6O18} clusters as ten-connected nodes, defining not only a new topology for three-periodic nets but also the first 6,10-connected framework using heterometallic clusters as nodes. Furthermore, the thermal stabilities and photocatalytic activities of 1–4 have been discussed in detail.

Assembly of Large Purely Inorganic Ce-Stabilized/Bridged Selenotungstates: From Nanoclusters to Layers

Co-reporter:Wei-Chao Chen; Chao Qin; Yang-Guang Li; Hong-Ying Zang;Kui-Zhan Shao; Zhong-Min Su; En-Bo Wang

Chemistry – An Asian Journal 2015 Volume 10( Issue 5) pp:1184-1191

Publication Date(Web):

DOI:10.1002/asia.201500004

Abstract

A versatile one-pot strategy was used to synthesize two large, purely inorganic selenotungstates, nanocluster K₆Na₁₆[Ce₆Se₆W₆₇O₂₃₀(OH)₆(H₂O)₁₇]⋅47 H₂O (1) and layer K₉Na₅Ce(H₂O)₄[Ce₆Se₁₀W₅₁O₁₈₇(OH)₇(H₂O)₁₈]⋅45 H₂O (2), by combining cerium centers and SeO₃²⁻ heteroanion templates. Compound 1 displays a Ce-stabilized hexameric nanocluster with one rhombus-like {W₄O₁₅(OH)₃} unit in the center, whereas compound 2 is the first example of a Ce-bridged layer selenotungstate network based on linkage of the unusual {Ce₆Se₁₀W₅₁O₁₈₇(OH)₇(H₂O)₁₈} clusters and additional Ce(H₂O)₄ fragments via Ce-O-Se bridges. The compounds were characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses, powder and single-crystal X-ray diffraction, and electrospray ionization mass spectrometry. Moreover, the electrochemical property of compound 1 was also investigated.

Cover Picture: Assembly of Large Purely Inorganic Ce-Stabilized/Bridged Selenotungstates: From Nanoclusters to Layers (Chem. Asian J. 5/2015)

Co-reporter:Wei-Chao Chen; Chao Qin; Yang-Guang Li; Hong-Ying Zang;Kui-Zhan Shao; Zhong-Min Su; En-Bo Wang

Chemistry – An Asian Journal 2015 Volume 10( Issue 5) pp:

Publication Date(Web):

DOI:10.1002/asia.201590014

A Stable Polyoxometalate-Pillared MetalOrganic Framework for Proton-Conducting and Colorimetric Biosensing

Co-reporter:Dr. En-Long Zhou; Chao Qin;Dr. Peng Huang; Xin-Long Wang;Dr. Wei-Chao Chen;Dr. Kui-Zhan Shao ; Zhong-Min Su

Chemistry - A European Journal 2015 Volume 21( Issue 33) pp:11894-11898

Publication Date(Web):

DOI:10.1002/chem.201501515

Abstract

A stable metal–organic framework pillared by Keggin-type polyoxometalate, Cu₆(Trz)₁₀(H₂O)₄[H₂SiW₁₂O₄₀]⋅8 H₂O (Trz=1,2,4-triazole) (1), has been prepared under hydrothermal condition. The 2D layer structure with a 22-member ring was formed by Cu²⁺ ions, which are connected with each other via the Trz ligands on the ab plane. Thus, the 2D layers are further interconnected through Keggin polyoxoanions to generate a 3D porous network with a small 1D channel. Moreover, the presence of polyoxoanions make it exhibit selective adsorption of water and proton-conducting properties. Additionally it showed efficient intrinsic peroxidase-like activity, providing a simple and sensitive colorimetric assay to detect H₂O₂.

A novel organic–inorganic hybrid constructed from the Nyman-type dititanoniobate [Ti2Nb8O28]8− and copper–organic cations

Co-reporter:Yu-Teng Zhang, Peng Huang, Chao Qin, Li-Kai Yan, Bai-Qiao Song, Zhao-Xia Yang, Kui-Zhan Shao and Zhong-Min Su

Dalton Transactions 2014 vol. 43(Issue 26) pp:9847-9850

Publication Date(Web):14 Apr 2014

DOI:10.1039/C4DT00507D

A new organic–inorganic hybrid titaniobate compound, [Cu(en)2][Cu(en)2(H2O)2]3[Ti2Nb8O28]·8H2O (1) (en = ethylenediamine), was successfully synthesized, characterized by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis (TGA) and UV-Vis diffuse reflectance spectroscopy and its photoluminescence studied.

Iodine-templated assembly of unprecedented 3d–4f metal–organic frameworks as photocatalysts for hydrogen generation

Co-reporter:Xiao-Li Hu, Chun-Yi Sun, Chao Qin, Xin-Long Wang, Hai-Ning Wang, En-Long Zhou, Wen-E Li and Zhong-Min Su

Chemical Communications 2013 vol. 49(Issue 34) pp:3564-3566

Publication Date(Web):14 Mar 2013

DOI:10.1039/C3CC39173F

Unprecedented 3d–4f MOFs encapsulating infinite linear polyiodide chains were firstly reported using iodine molecules as a versatile precursor template. They possess high framework stability in acid/base aqueous solutions. The kinetics of iodine molecule release/recovery and UV-light photocatalytic H2 evolution activities were investigated.

A series of coordination complexes based on unsymmetrical multicarboxylate ligands: syntheses, structures and properties

Co-reporter:Dong-Hua Hu, Chun-Yi Sun, Fu-Hong Liu, Chao Qin, Xin-Long Wang and Zhong-Min Su

CrystEngComm 2013 vol. 15(Issue 34) pp:6769-6775

Publication Date(Web):05 Jul 2013

DOI:10.1039/C3CE40782A

Six new coordination polymers, namely, [Zn2(L1)2phen2(H2O)2] (1), [M3(L1)2(OH)2 (4,4′-bpy)(H2O)2]·2H2O (M = Cd (2), Co(3)), [Cd5(L1)2(OH)2(trz)4(L3)]·2H2O (4), [Zn(HL2)(4,4′-bpy)] (5) and [Cd3(L2)2(L3)2(H2O)5]·H2O (6) (H2L1 = 4-(1-carboxy-ethoxy)-benzoic acid, H3L2 = 5-(1-carboxy-ethoxy)-isophthalic acid, L3 = 1,2-bis(1,2,4-triazole-1-yl)ethane, phen = 1,10-phenanthroline, 4,4′-bpy = 4,4′-bipyridine, Htrz = 1,2,4-triazole), have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compound 1 is a molecular square composed by two Zn ions, two L1 and two phen ligands. Compounds 2 and 3 are isostructural and display 3D frameworks constructed by 1D M–O–M chains. Compound 4 exhibits a 3D 8-connected network with hex topology based on the pentanuclear Cd cluster and the point symbol is (36·418·53·6). Compound 5 shows a 2D wavelike layer with sql topology. Compound 6 reveals a 3D three-fold interpenetrating architecture having (3,4)-connected dmd topology with the point symbol of (4·102)2(42·104). These compounds have been characterized by infrared spectroscopy (IR) and thermal gravimetric analyses (TGA). In addition, the photoluminescent behaviour of 1, 2, and 4–6 has been investigated in detail.

Serendipitous anion-templated self-assembly of a sandwich-like Ag20S10 macrocycle-based high-nuclearity luminescent nanocluster

Co-reporter:Kun Zhou, Xin-Long Wang, Chao Qin, Hai-Ning Wang, Guang-Sheng Yang, Yan-Qing Jiao, Peng Huang, Kui-Zhan Shao and Zhong-Min Su

Dalton Transactions 2013 vol. 42(Issue 5) pp:1352-1355

Publication Date(Web):15 Nov 2012

DOI:10.1039/C2DT32145A

The first macrocycle-based high-nuclearity nanocluster [Ag20(StBu)10(CF3COO)2]8+ in complex 1, with a sandwich-like structure constructed by bilevel inversion Ag5S5 pentagrams and an interlayer Ag10 ring, has been obtained. Structure analysis indicates that Cl− acts as an anion template to direct the formation of 1. In addition, the photoluminescent property of complex 1 is also investigated.

Two layered copper–bis(triazole) assemblies with Keggin polyoxoanions as pendants: Syntheses, structures and photocatalytic properties

Co-reporter:Nan Wu, Ying Qin, Xin-Long Wang, Chao Qin, En-Bo Wang

Inorganic Chemistry Communications 2013 Volume 37() pp:174-177

Publication Date(Web):November 2013

DOI:10.1016/j.inoche.2013.09.072

•We report two layered assemblies with Keggin polyoxoanions as pendants.•The photocatalytic properties were studied upon UV irradiation.•Two complexes show superior photocatalytic activity in the reduction of organic dye.Two new inorganic–organic hybrid compounds based on well-defined Keggin-type polyoxometalates and copper–bis(triazole) assemblies, namely, [Cu3(L)3(PMo12O40)2] · 9H2O (1) and [Cu3(L)3(PW12O40)2] · 9H2O (2) [L = 1,4-bis(1,2,4-triazol-1-ylmethyl)-benzene], have been obtained under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, IR, and TG. To the best of our knowledge, compounds 1 and 2 represent rare 2D structural examples with POM clusters as pendants. In addition, the diffuse reflectivity spectra of these two compounds show that they can be regarded as a wide gap semiconductor. The photocatalytic experiments indicate that both 1 and 2 exhibit high catalytic activity for photodegradation of Rhodamine B (RhB) with UV irradiation.Two layered copper–bis(triazole) assemblies with Keggin polyoxoanions as pendants are presented that exhibit high catalytic activity for photodegradation of rhodamine B with UV irradiation.

Solvatochromic Behavior of Chiral Mesoporous MetalOrganic Frameworks and Their Applications for Sensing Small Molecules and Separating Cationic Dyes

Co-reporter:Dr. Chun-Yi Sun; Xin-Long Wang;Jun-Ling Jin;Zhong-Min Su;Peng Huang ;Kui-Zhan Shao

Chemistry - A European Journal 2013 Volume 19( Issue 11) pp:3639-3645

Publication Date(Web):

DOI:10.1002/chem.201203080

Abstract

Two anionic metal–organic frameworks (MOFs) with 1D mesoporous tubes (1) and chiral mesoporous cages (2) have been rationally constructed by means of a predesigned size-extended hexatopic ligand, namely, 5,5′,5′′-(1,3,5-triazine-2,4,6-triyl)tris- (azanediyl)triisophthalate (TATAT). Charge neutrality is achieved by protonated dimethylamine cations. Notably, the two MOFs can be used to separate large molecules based on ionic selectivity rather than the size-exclusion effect so far reported in the literature. Owing to the imino triazine backbone and carboxyl groups of the hexatopic ligand, which provide important host–guest interactions, rare solvatochromic phenomena of 1 and 2 are observed on incorporating acetone and ethanol guests. Furthermore, guest-dependent luminescence properties of compound 2 were investigated, and the results show that luminescence intensity is significantly enhanced in toluene and benzene, while quenching effects are observed in acetone and ethanol. Thus, compound 2 may be a potential material for luminescent probes.

An Ionothermal Synthetic Approach to Porous Polyoxometalate-Based MetalOrganic Frameworks

Co-reporter:Dr. Hai Fu; Chao Qin; Ying Lu;Dr. Zhi-Ming Zhang; Yang-Guang Li; Zhong-Min Su;Dr. Wen-Liang Li ; En-Bo Wang

Angewandte Chemie International Edition 2012 Volume 51( Issue 32) pp:7985-7989

Publication Date(Web):

DOI:10.1002/anie.201202994

An Ionothermal Synthetic Approach to Porous Polyoxometalate-Based MetalOrganic Frameworks

Co-reporter:Dr. Hai Fu; Chao Qin; Ying Lu;Dr. Zhi-Ming Zhang; Yang-Guang Li; Zhong-Min Su;Dr. Wen-Liang Li ; En-Bo Wang

Angewandte Chemie 2012 Volume 124( Issue 32) pp:8109-8113

Publication Date(Web):

DOI:10.1002/ange.201202994

A novel organic–inorganic hybrid constructed from the Nyman-type dititanoniobate [Ti2Nb8O28]8− and copper–organic cations

Co-reporter:Yu-Teng Zhang, Peng Huang, Chao Qin, Li-Kai Yan, Bai-Qiao Song, Zhao-Xia Yang, Kui-Zhan Shao and Zhong-Min Su

Dalton Transactions 2014 - vol. 43(Issue 26) pp:NaN9850-9850

Publication Date(Web):2014/04/14

DOI:10.1039/C4DT00507D

A new organic–inorganic hybrid titaniobate compound, [Cu(en)2][Cu(en)2(H2O)2]3[Ti2Nb8O28]·8H2O (1) (en = ethylenediamine), was successfully synthesized, characterized by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis (TGA) and UV-Vis diffuse reflectance spectroscopy and its photoluminescence studied.

Spontaneous chiral resolution of a rare 3D self-penetration coordination polymer for sensitive aqueous-phase detection of picric acid

Co-reporter:Bai-Qiao Song, Chao Qin, Yu-Teng Zhang, Xue-Song Wu, Liu Yang, Kui-Zhan Shao and Zhong-Min Su

Dalton Transactions 2015 - vol. 44(Issue 42) pp:NaN18394-18394

Publication Date(Web):2015/09/09

DOI:10.1039/C5DT03218K

Two unprecedented homochiral enantiomers based on two different kinds of rigid ligands, namely [Cd(NDC)L]2·H2O (1R and 1L), have been synthesized under hydrothermal conditions through spontaneous resolution. Their structures were determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR, and thermogravimetric (TG) analysis. The resulting framework 1, constructed by four kinds of homo-handed helical chains represents the first 3D self-penetrating framework formed by decoration of single (10,3)-a net with helical chains. The single (10,3)-a net in 1 formed by three kinds of different homo-handed helical chains is different from the standard one, which should be ascribed to the usage of V-shaped ligand L. A unique self-penetration motif can be discovered in 1 where one helical chain alternately passes through 10-membered shortest circuits linked to each other and in contrary, the corresponding circuits are bound to the helical chain. Interestingly, 1 exhibits fluorescent emission in both the solid and solution phase. The uncoordinated nitrogen atom and amino group from the triazole core on the crystal surface make it suitable to detect picric acid in water. The luminescence intensity of 1 in water can be efficiently quenched by the addition of picric acid (PA). The sensitive detection of PA can be continuously performed for at least five cycles without diminishing the fluorescence intensity and destroying the framework structure of 1. The possible quenching mechanisms for PA are also investigated.

Pillared metal organic frameworks for the luminescence sensing of small molecules and metal ions in aqueous solutions

Co-reporter:Fu-Hong Liu, Chao Qin, Yan Ding, Han Wu, Kui-Zhan Shao and Zhong-Min Su

Dalton Transactions 2015 - vol. 44(Issue 4) pp:NaN1760-1760

Publication Date(Web):2014/11/17

DOI:10.1039/C4DT02961E

Two novel pillared MOFs (metal organic frameworks) [Zn2(trz)2(tda)]·DMA CH3OH (1) and [Zn2(trz)2(bpdc)]·DMA (2) were obtained under solvothermal conditions. The resulting MOFs show similar structures but with different interlayer distances based on the different carboxylate ligands. 1 and 2 display a certain degree of framework stability in both acid/base solutions and water. The luminescence intensities of the activated phases 1a and 2a are sensitive to metal ions, particularly Fe3+ and Cd2+ ions. Furthermore, the luminescent properties of 1a and 2a well dispersed in different solvents have also been investigated systematically, which demonstrate distinct solvent-dependent luminescent spectra with emission intensities that are significantly quenched by acetone, nitrobenzene and trinitrotoluene.

Iodine-templated assembly of unprecedented 3d–4f metal–organic frameworks as photocatalysts for hydrogen generation

Co-reporter:Xiao-Li Hu, Chun-Yi Sun, Chao Qin, Xin-Long Wang, Hai-Ning Wang, En-Long Zhou, Wen-E Li and Zhong-Min Su

Chemical Communications 2013 - vol. 49(Issue 34) pp:NaN3566-3566

Publication Date(Web):2013/03/14

DOI:10.1039/C3CC39173F

Unprecedented 3d–4f MOFs encapsulating infinite linear polyiodide chains were firstly reported using iodine molecules as a versatile precursor template. They possess high framework stability in acid/base aqueous solutions. The kinetics of iodine molecule release/recovery and UV-light photocatalytic H2 evolution activities were investigated.

A stable luminescent anionic porous metal–organic framework for moderate adsorption of CO2 and selective detection of nitro explosives

Co-reporter:En-Long Zhou, Peng Huang, Chao Qin, Kui-Zhan Shao and Zhong-Min Su

Journal of Materials Chemistry A 2015 - vol. 3(Issue 14) pp:NaN7228-7228

Publication Date(Web):2015/03/02

DOI:10.1039/C5TA00231A

A stable luminescent anionic metal–organic framework with unprecedented topological structure was constructed, which showed a certain degree of framework stability in water and acid/base solutions. Furthermore, the compound showed moderate CO2 adsorption and extremely selective detection of 2,4,6-trinitrophenol (TNP) in both an organic solvent and aqueous solution.

Serendipitous anion-templated self-assembly of a sandwich-like Ag20S10 macrocycle-based high-nuclearity luminescent nanocluster

Co-reporter:Kun Zhou, Xin-Long Wang, Chao Qin, Hai-Ning Wang, Guang-Sheng Yang, Yan-Qing Jiao, Peng Huang, Kui-Zhan Shao and Zhong-Min Su

Dalton Transactions 2013 - vol. 42(Issue 5) pp:NaN1355-1355

Publication Date(Web):2012/11/15

DOI:10.1039/C2DT32145A

The first macrocycle-based high-nuclearity nanocluster [Ag20(StBu)10(CF3COO)2]8+ in complex 1, with a sandwich-like structure constructed by bilevel inversion Ag5S5 pentagrams and an interlayer Ag10 ring, has been obtained. Structure analysis indicates that Cl− acts as an anion template to direct the formation of 1. In addition, the photoluminescent property of complex 1 is also investigated.

A 2D bilayered metal–organic framework as a fluorescent sensor for highly selective sensing of nitro explosives

Co-reporter:Xiao-Li Hu, Fu-Hong Liu, Chao Qin, Kui-Zhan Shao and Zhong-Min Su

Dalton Transactions 2015 - vol. 44(Issue 17) pp:NaN7827-7827

Publication Date(Web):2015/03/19

DOI:10.1039/C5DT00515A

A novel Cd-MOF (metal organic framework) [Cd3(NTB)2(DMA)3]·2DMA (H3NTB = 4,4′,4′′-nitrilotrisbenzoic acid; DMA = N,N-dimethylacetamide) (1) was obtained under solvothermal conditions. The resulting MOF exhibits a novel (2D→3D) interdigitated architecture that is obtained from a bilayered motif with hexagonal grids. Luminescence properties of the activated phase of 1a well dispersed in different solvents have also been investigated systematically, which demonstrate distinct solvent-dependent luminescence spectra with emission intensities significantly quenched toward nitrobenzene (NB) and 2,4,6-trinitrophenol (TNP). The results reveal that 1 can be applied as a fluorescent sensor for the detection of TNP with high sensitivity, selectivity, and recyclability.

A novel [4 + 3] interpenetrated net containing 7-fold interlocking pseudo-helical chains and exceptional catenane-like motifs

Co-reporter:Bai-Qiao Song, Chao Qin, Yu-Teng Zhang, Li-Tao An, Kui-Zhan Shao and Zhong-Min Su

Dalton Transactions 2015 - vol. 44(Issue 6) pp:NaN2851-2851

Publication Date(Web):2014/10/22

DOI:10.1039/C4DT02808B

A novel interpenetrating metal–organic framework, namely [Zn3L2(oba)3(H2O)2]·4H2O (1), has been synthesized under hydrothermal conditions. Its structure was determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR, and thermogravimetric (TG) analysis. In the structure of 1, the rigid and flexible V-shaped ligands link Zn(II) to form a 3D structure where two types of helices and four types of pseudo-helical chains containing three pairs of enantiomers and two pairs of conformational isomers have been characterized. One such 3D framework incorporates six identical networks to form a 7-fold interpenetrated 3D framework. From the topological analysis, the Zn(II) ions act as three- and four-connected nodes, and oba as well as L are linkers. The framework of compound 1 can be classified as a new (63)2(65·8) topology, which is a novel (3,3,4)-connected [4 + 3] 7-fold interpenetrating net showing 7-fold interlocking pseudo-helical chains and a unique catenane-like motif with Hopf links. In addition, the luminescence properties of the compound are discussed.

A luminescent dye@MOF as a dual-emitting platform for sensing explosives

Co-reporter:Xiao-Li Hu, Chao Qin, Xin-Long Wang, Kui-Zhan Shao and Zhong-Min Su

Chemical Communications 2015 - vol. 51(Issue 99) pp:NaN17524-17524

Publication Date(Web):2015/09/23

DOI:10.1039/C5CC07004J

An anionic metal–organic framework (MOF) with 1D nanotube channels has been constructed. The charge and size dependent ion-exchange of cationic dyes was investigated. Rho@1 could be used as a dual-emitting fluorescent sensor for sensing explosives by self-referencing energy transfer behaviors.

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