Co-reporter:Chen Yang, Ming-Sheng Wang, Zhong-Ning Xu, Feng Chen, Guang-Ning Liu, Gang Xu, Guo-Cong Guo, Jin-Shun Huang
Inorganic Chemistry Communications 2010 Volume 13(Issue 2) pp:326-329
Publication Date(Web):February 2010
DOI:10.1016/j.inoche.2009.12.017
Compared to previously reported methods, a less hazardous approach has been used to synthesize N-methylpyrazinium cation (mpz+) by the reaction of pyrazine and ClCH2COONa. Although a few mpz+-containing complexes have been documented, there is no example of mpz+-containing group IIB metal complexes. Three novel complexes containing mpz+, (mpz)ZnI3 (1), [(mpz)CdCl3]n (2), and [(mpz)CdBr3]n (3), have been successfully obtained via a solution or hydrothermal method by reactions of ZnI2, CdCl2·2.5H2O, and CdBr2·4H2O with the mpz+ ligand, respectively. Complex 1 features an isolated structure, with each zinc atom coordinated by one mpz+ ligand and three terminal iodine atoms. The CD spectra of 1 reveal that it exhibits spontaneous resolution. Complexes 2 and 3 are isotypic, and exhibit chain structures made by linear arrays of Cd(II) bridged by halogen atoms. Photoluminescent analyses reveal that complexes 1–3 exhibit strong blue emissions originating from intra-ligand π–π∗ transition of the mpz+ ligand.A less hazardous approach has been used to synthesize N-methylpyrazinium cation ligand (mpz+). Three novel mpz+-containing complexes with interesting structural modes have been successfully obtained. Photoluminescent analyses reveal that three complexes exhibit strong blue emissions originating from intra-ligand π–π∗ transition of the ligand.
Co-reporter:Chen Yang, Ming-Sheng Wang, Li-Zhen Cai, Xiao-Ming Jiang, Mei-Feng Wu, Guo-Cong Guo, Jin-Shun Huang
Inorganic Chemistry Communications 2010 Volume 13(Issue 9) pp:1021-1024
Publication Date(Web):September 2010
DOI:10.1016/j.inoche.2010.05.020
A new approach has been used to synthesize MQ+ ligand (MQ+ = N-methyl-4,4′-bipyridinium) by the reaction of 4,4′-bipyridine and chloroacetic acid, and the structure of (MQ)Cl·H2O (1) was first determined. Three new complexes containing MQ+, (MQ)CdI3 (2), (MQ)ZnI3 (3), and [(MQ)ZnCl1.53I1.47]2(MQ)ZnCl1.68I1.32 (4), were successfully obtained via a solution or hydrothermal method by reaction of MI2 (M = Cd, Zn) with 1, and each of which exhibits an isolated structure, with each metal atom coordinated by one MQ+ ligand and three terminal halogen atoms. Compounds 123–4 all display photoluminescence in the visible region under visible-light excitation, and the origins of the emissions have been assigned to ILCT for 1 and the combination of ILCT and LLCT for 23–4.A new approach has been used to synthesize N-methyl-4,4′-bipyridinium cation ligand (MQ+). Three novel MQ+-containing complexes have been successfully obtained. These compounds all display photoluminescence in the visible region under visible-light excitation, and the origins of the emissions have been discussed.
Co-reporter:Jian-Ping Zou;Yan Li;Ming-Lai Fu;Gang Xu;Xue-Hui Liu;Wei-Wei Zhou;Jin-Shun Huang
European Journal of Inorganic Chemistry 2007 Volume 2007(Issue 7) pp:
Publication Date(Web):16 JAN 2007
DOI:10.1002/ejic.200600894
The series of supramolecular complexes (Hg6As4)(CdCl6)Hg0.5 (1), (Hg6As4)(HgCl6)Hg0.5 (2), (Hg6As4)(CdBr6) (3), and (Hg6Sb4)(CdI6)Hg0.6 (4) has been prepared by a solid-state reaction and their crystal structures determined by single-crystal X-ray diffraction. All these compounds crystallize in the space group Pa with four formula units in a cell: a = 12.172(2) (1), 12.189(1) (2), 12.3738(5) (3), and 13.234(2) Å (4). Their structures feature a 3D cationic host framework that is built up of linearly coordinated mercury and tetrahedrally coordinated pnicogen atoms to form distorted As2Hg6 or Sb2Hg6 octahedra, and discrete guest anions. The distorted octahedra corner-share with each other to form a perovskite-like, 3D cationic framework that possess two types of closed cavities with different sizes. The octahedral guest anions (MX6)4– are embedded in the larger cavities, whereas the smaller cavities trap the excess mercury atoms or remain empty. The optical properties were investigated by diffuse reflectance and FT IR spectroscopy. The electronic band structures and density of states (DOS) calculated by DFT methods indicate that the present compounds are semiconductors and that the optical absorption mainly originates from the charge transitions from the p orbital of the pnicogen (As or Sb) and halogen (Cl, Br or I) atoms states to the Hg1 6s states for 1, 3, and 4, and to Hg1 6s and Hg3 6sstates for 2.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Co-reporter:Jian-Ping Zou, Dong-Sheng Wu, Shu-Ping Huang, Jing Zhu, Guo-Cong Guo, Jin-Shun Huang
Journal of Solid State Chemistry 2007 Volume 180(Issue 3) pp:805-811
Publication Date(Web):March 2007
DOI:10.1016/j.jssc.2006.11.018
A new quaternary supramolecular complex (Hg2As)2 (CdI4) (1) has been prepared by the solid-state reaction and structurally characterized by single crystal X-ray diffraction analysis. Compound 1 crystallizes in the space group P21 of the monoclinic system with two formula units in a cell: a=7.945(4), b=12.934(6), c=8.094(4) Å, β=116.898°(1), V=741.7(6) Å3. The structure of 1 is characterized by a tridymite-like three-dimensional cationic framework, which is composed of mercury and arsenic atoms, with the channels being occupied by discrete CdI42− tetrahedral guest-anions. The optical properties were investigated in terms of the diffuse reflectance and Fourier transform infrared spectra. The electronic band structure along with density of states (DOS) calculated by DFT method indicates that the present compound is a semiconductor with a direct band gap, and that the optical absorption is mainly originated from the charge transitions from I-5p and As-4p to Cd-5s and Hg-6s states.A new quaternary supramolecular complex (Hg2As)2(CdI4) (1) has been prepared by the solid-state reaction, and structurally characterized by single crystal X-ray diffraction analysis. The structure of 1 is characterized by a 3-D tridymite-like cationic framework with the channels being occupied by discrete CdI42− tetrahedral guest-anions.
Co-reporter:Gang Xu Dr.;Ming-Sheng Wang Dr.;Zhang-Jing Zhang;Wen-Tong Chen Dr.;Jin-Shun Huang
Angewandte Chemie International Edition 2007 Volume 46(Issue 18) pp:
Publication Date(Web):27 MAR 2007
DOI:10.1002/anie.200700122
Color scheme: Reversibly photochromic crystals of (MV)Bi2Cl8 (methyl viologen, MV2+: N,N′-dimethyl-4,4′-bipyridinium) show structural variations before and after UV irradiation. Color reversion is accomplished by heating in air (see picture). ([Bi2Cl8]2−)∞ double-octahedral chains serve as electron donors to in situ generated MV2+ dications.
Co-reporter:Ming-Sheng Wang Dr. Dr.;Wen-Tong Chen;Gang Xu;Wei-Wei Zhou;Ke-Jun Wu;Jin-Shun Huang
Angewandte Chemie 2007 Volume 119(Issue 21) pp:
Publication Date(Web):19 APR 2007
DOI:10.1002/ange.200604946
Intrinsisch weiße Boratleuchtstoffe: Die Solvothermalreaktion von H3BO3 und Ethylendiamin lieferte das erste dreidimensionale zeolithartige Ammoniumborat. Seine blaue Photolumineszenz lässt sich durch einfache Wärmebehandlung bei 250, bei 360 oder bei 250 °C nach Dotierung mit Eu3+-Ionen in weiß überführen (von links nach rechts im Bild). Ohne Lösungsmittel lieferte dieselbe Solvothermalreaktion das erste Gerüst mit Boratschichten und Aminsäulen.
Co-reporter:Gang Xu Dr.;Ming-Sheng Wang Dr.;Zhang-Jing Zhang;Wen-Tong Chen Dr.;Jin-Shun Huang
Angewandte Chemie 2007 Volume 119(Issue 18) pp:
Publication Date(Web):27 MAR 2007
DOI:10.1002/ange.200700122
Farbspiele: Die Sturktur reversibel photochromer Kristalle von (MV)Bi2Cl8 (MV2+: N,N′-Dimethyl-4,4′-bipyridinium; Methylviologen) ändert sich durch UV-Bestrahlung. Durch Erhitzen an Luft kann die ursprüngliche Farbe wiederhergestellt werden (siehe Bild). ([Bi2Cl8]2−)∞-Ketten aus Dioktaedereinheiten übertragen Elektronen auf die in situ erzeugten Dikationen MV2+.
Co-reporter:Ming-Sheng Wang Dr. Dr.;Wen-Tong Chen;Gang Xu;Wei-Wei Zhou;Ke-Jun Wu;Jin-Shun Huang
Angewandte Chemie International Edition 2007 Volume 46(Issue 21) pp:
Publication Date(Web):19 APR 2007
DOI:10.1002/anie.200604946
Intrinsic white borate phosphors: Solvothermal reaction of H3BO3 and ethylenediamine afforded the first three-dimensional zeolite-like ammonium borate. Its blue photoluminescence can be modified to white by a simple heat-treatment process at 250, at 360, or at 250 °C after doping with Eu3+ ions (see picture, left to right). In the absence of solvent, the same solvothermal reaction gave the first amine-pillared layer borate-based framework.
Co-reporter:Xi Liu, Guo-Cong Guo, Ming-Lai Fu, Wen-Tong Chen, Zhang-Jing Zhang and Jin-Shun Huang
Dalton Transactions 2006 (Issue 7) pp:884-886
Publication Date(Web):24 Nov 2005
DOI:10.1039/B515652C
The reactions of silver(I) cyanide with tetraalkylammonium salts in anhydrous tetrahydrofuran (THF) under solvothermal conditions and then diffused with ether lead to two novel mixed halogeno(cyano)argentates(I) with efficient luminescence.
Co-reporter:Wen-Tong Chen, Ming-Sheng Wang, Zhang-Jing Zhang, Gang Xu, Guo-Cong Guo, Jin-Shun Huang
Journal of Solid State Chemistry 2006 Volume 179(Issue 11) pp:3394-3399
Publication Date(Web):November 2006
DOI:10.1016/j.jssc.2006.07.006
Two isostructural metal chalcogenides, Hg2Te2Br2 (1) and Hg2Te2I2 (2), were obtained by solid-state reactions and structurally characterized. Compounds 1 and 2 crystallize in the acentric space group P43212 of the tetragonal system with eight formula units in a cell: a=10.2388(9), c=14.480(2) Å, V=1518.0(3) Å3, R1/wR2=0.0670/0.1328 for 1 and a=10.711(3), c=15.025(8) Å, V=1724(1) Å3, R1/wR2=0.0637/0.1233 for 2. Both compounds are characterized by a three-dimensional (3-D) framework structure, which is composed by interconnected left-handed helices formed by both tetrahedral and trigonal Hg atoms. Optical absorption spectra of 1 and 2 reveal the presence of sharp optical gaps of 2.06 and 1.85 eV, respectively, suggesting that both materials are semiconductors. TG-DTA measurements show that both compounds are thermally stable up to 200 °C. The composition of both compounds is well confirmed by the semiquantitative microscope analyses.A new family of IIB2Q2X2 system, possessing an acentric nature that allows them to be a potential NLO material, has been synthesized via solid-state reactions. The crystal structures are characterized by a 3-D framework structure, comprising of interconnected left-handed helices. Optical absorption spectra show that both compounds are excellent candidate for potential photoelectric materials.
Co-reporter:Qiang Li, Xi Liu, Ming-Lai Fu, Guo-Cong Guo, Jin-Shun Huang
Inorganica Chimica Acta 2006 Volume 359(Issue 7) pp:2147-2153
Publication Date(Web):25 April 2006
DOI:10.1016/j.ica.2006.01.010
Systematic survey on the reactions of silver nitrate with H3Ssal ligand (H3Ssal = 5-sulfo-salicylic acid) accompanying with different alkali metal ions under alkali conditions leads to two novel luminescent alkali-silver heterometallic sulfonates, [KAg(HSsal)(H2O)3]n (1) with a 3-D structure constructed by [K2O10] binuclear units linking 1-D∞1[Ag2(HSsal)2] double chains, [NaAg(HSsal)(H2O)3]n (2) with a 3-D structure constructed by the [Ag2(HSsal)2] dimers connecting 1-D∞1[NaO6] chains, and also reveals the coordination strength of the alkali metal cations and Ag+ towards the sulfonate groups with K+ > Na+ > Ag+ > Li+ order. The two compounds show intense blue emissions in both solid state and water solution.Systematic survey on the reactions of silver nitrate with H3Ssal ligand accompanying with different alkali metal ions under alkali conditions leads to two novel luminescent alkali-silver heterometallic sulfonates, and also reveals the coordination strength of the alkali metal cations and Ag+ towards the sulfonate groups with K+ > Na+ > Ag+ > Li+ order.
Co-reporter:Xi Liu, Guo-Cong Guo, Ming-Lai Fu, Jian-Ping Zou, Fa-Kun Zheng, Jin-Shun Huang
Inorganica Chimica Acta 2006 Volume 359(Issue 5) pp:1643-1649
Publication Date(Web):20 March 2006
DOI:10.1016/j.ica.2005.12.038
Spontaneous resolution in solvothermal reactions through tuning the volume of the templating and space-filling agents (quaternary ammonium cations) lead to three novel halogeno(cyano)cuprates [R4N][Cu(CN)X] (R = Et, X = Cl, 1; R = Et, X = Br, 2; R = Bu, X = I, 3), which all consist of 1-D helical chains. Compounds 1 and 2 reveal to be mesomeric structures while compound 3 exhibits a nonracemic enantiopure topology. Luminescent studies indicate that all three compounds are potential materials for efficient luminescent materials.Spontaneous resolution in solvothermal reactions through tuning the volume of the templating and space-filling agents (quaternary ammonium cations) lead to two racemic and one novel nonracemic enantiopure halogeno(cyano)cuprates, which all exhibit efficient luminescence.
Co-reporter:Bing Liu, Guo-Cong Guo, Jin-Shun Huang
Journal of Solid State Chemistry 2006 Volume 179(Issue 10) pp:3136-3144
Publication Date(Web):October 2006
DOI:10.1016/j.jssc.2006.05.046
Four triazole-bridging coordination complexes, [Zn4(ptr)2(SO4)3(μ3-OH)2(H2O)4]n (1), [Hg(CN)2(ptr)]n (2), [Hg(Cl)2(ptr)]n (3), and [Cu2(μ2-ptr)2(μ2-F)2]n(SiF6)n·2nH2O (4), were synthesized with (m-phenol)-1,2,4-triazole (ptr). Compounds 1–4 with extended structures of 4-substituted 1,2,4-triazole are rarely reported. The layered structure of 1 can be regarded as constructed from the 2-D inorganic backbone of SO42−(2) anions bridging [Zn4(μ3-OH)2(H2O)2]6− subunits with the ptr ligands anchoring to both sides of backbone. Compounds 2 and 3 are the first mercury(II) complexes with 4-substituted 1,2,4-triazole, which feature the ptr ligand acting as a bidentate ligand bridging the Hg(II) atoms to form arciform –Hg–ptr–Hg–ptr chains. The structure of 4 is constructed from the F atoms bridging Cu atoms in symmetrical μ2-coordination mode to form a zigzag cationic chain with each ptr ligand bridging a pair of Cu atom on the both sides, resulting in a nonplanar 5-membered [Cu2N2F] ring. Fluorescent properties of 1–4 were characterized and the magnetic property of 4 shows antiferromagnetic interaction between the copper(II) ions.Four triazole-bridging coordination complexes, [Zn4(ptr)2(SO4)3(μ3-OH)2(H2O)4]n (1), [Hg(CN)2(ptr)]n (2), [Hg(Cl)2(ptr)]n (3) and [Cu2(μ2-ptr)2(μ2-F)2]n(SiF6)n·2nH2O (4), were synthesized with (m-phenol)-1,2,4-triazole (ptr). Compounds 1–4 with extended structures of 4-substituted 1,2,4-triazole are rarely reported.
Co-reporter:A-Qing Wu;Guang-Hua Guo;Chun Yang;Fa-Kun Zheng;Xi Liu;Jin-Shun Huang;Zhen-Chao Dong;Yoshihiko Takano
European Journal of Inorganic Chemistry 2005 Volume 2005(Issue 10) pp:
Publication Date(Web):18 MAY 2005
DOI:10.1002/ejic.200400679
The first examples of 3d–4f heterometallic complexes containing picolinic acid ligands were synthesized and characterized. Three series of complexes were obtained by the reaction of presynthesized “metallo ligands” Cu(pic)2 and Ln(ClO4)3 in 2:1, 3:1, and 4:1 mole ratios. Complexes 1–3(denoted as the first series), [LnCu2(pic)4(H2O)6](ClO4)3·H2O (Ln = Sm, Nd, and Pr), are isomorphous and exhibit infinite 1D zigzag chain structures with rare earth ions in tricapped trigonal prismatic coordination. Complexes 4–10 (denoted as the second series), [Ln2Cu5(pic)10(H2O)8](ClO4)6·2H2O (Ln = Gd, Nd, Sm, Dy, Eu, Pr, and Yb), are isomorphous too, and exhibit extended 2D layered structures constituted by Cu(pic)2 moieties bridging the zigzag chains. Complex 11(denoted as the third-type complex), {NdCu(pic)2[CO(NH2)2]4(H2O)3}(ClO4)3·[Cu(pic)2]2, exhibits another type of nearly linear chain structure with additional Cu(pic)2 moieties trapped in the lattice by hydrogen bonds. Temperature-dependent magnetizations of complexes 2–4, 6, and 11 indicate that these complexes follow the Curie–Weiss paramagnetic behavior down to 5 K. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Co-reporter:Ming-Lai Fu;A-Qing Wu;Bin Liu;Li-Zhen Cai;Jin-Shun Huang
European Journal of Inorganic Chemistry 2005 Volume 2005(Issue 15) pp:
Publication Date(Web):22 JUN 2005
DOI:10.1002/ejic.200500055
The novel chiral mixed-valence vanadium oxide hybrid [V5O11(dien)3] (1) (dien = NH2C2H4NHC2H4NH2) has been synthesised by a hydrothermal reaction of V2O5 and dien in aqueous solution and characterised by elemental analysis, IR spectroscopy, TG-DSC analysis, magnetism, EPR spectroscopy, single-crystal X-ray diffraction and powder XRD. The X-ray diffraction analysis revealed that the structure of 1 can be regarded as being constructed from two [VVO4]3– groups bicapping three [VIVO(dien)]2+ units to form a discrete asymmetric pentanuclear vanadium complex with the dien ligands coordinating directly to the vanadium(IV) centres. Compound 1 exhibits an interesting tube-like 3D supramolecular structure due to abundant hydrogen-bonding interactions between the oxygen atoms of the inorganic backbone and the hydrogen atoms of the dien ligands from adjacent molecules. The variable-temperature magnetic susceptibility data of 1 suggest a weak ferromagnetic interaction among V4+ ions in the cluster. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Co-reporter:Ling Xu, Bing Liu, Fa-Kun Zheng, Guo-Cong Guo, Jin-Shun Huang
Journal of Solid State Chemistry 2005 Volume 178(Issue 11) pp:3396-3404
Publication Date(Web):November 2005
DOI:10.1016/j.jssc.2005.08.024
Three new zinc coordination polymers [Zn2(btc)2(H2O)2]n·n[Zn(H2O)6] (1), [Zn3(btc)2(2,2′-bipy)2(H2O)3]n·2nH2O (2) and [Zn3(btc)2(H2O)6]n·nH2O (3) (H3btc=1,2,4-benzenetricarboxylic acid, 2,2′-bipy=2,2′-bipyridine) were obtained by the diffusion method and their crystal structures were determined by single-crystal X-ray diffraction. Compounds 1–3 have the similar tetrametallic unit [Zn4(btc)2] SBUs and these SBUs are further connected into stair-like structure, 2-D layer and 3-D framework for 1, 2 and 3, in which the btc3− ligands adopt μ3, μ4 and μ5 coordination modes, respectively. The title compounds show strong blue fluorescence, which may be assigned as π*→n transition of the ligand mixed with the ligand-to-metal change transfer (LMCT), indicating the fluorescence, indicates the title compounds may be good candidates for blue-light photoactive materials.Three new zinc metal-organic polymers with different modes (μ3, μ4, μ5) of btc3− ligand were obtained from diffusion method, which are constructed from the similar tetrametallic unit [Zn4(btc)2] SBUs. All the title compounds show strong blue fluorescence and the fluorescence may be related to the π*→n transition of the ligand mixed with the ligand-to-metal change transfer (LMCT).
Co-reporter:Ming-Sheng Wang, Guo-Cong Guo, Li-Zhen Cai, Wen-Tong Chen, Bing Liu, A-Qing Wu and Jin-Shun Huang
Dalton Transactions 2004 (Issue 15) pp:2230-2236
Publication Date(Web):28 Jun 2004
DOI:10.1039/B405323K
Five zinc complexes of T-shaped trans-1,2,3-propenetricarboxylic acid (H3L) with 1-D ribbon-like chain, 2-D rhombus-grid-like and herringbone-like layers, and non-interpenetrating 3-D open framework have been obtained based on different building blocks. X-ray single crystal analyses show that the T-shaped information of H3L was nicely expressed in the construction of herringbone-like or ladder-like structure. All compounds were found to display blue fluorescent emissions.
Co-reporter:Xing Zhang, Guo-Cong Guo, Fa-Kun Zheng, Guo-Wei Zhou, Jiang-Gao Mao, Zhen-Chao Dong, Jin-Shun Huang and Thomas C. W. Mak
Dalton Transactions 2002 (Issue 7) pp:1344-1349
Publication Date(Web):08 Mar 2002
DOI:10.1039/B109298G
Three coordination polymers, [Ag4(L1)2(NO3)4]·H2O (1), [Ag(L1)](BF4)·2H2O (2) and [Ag2(L1)(H2O)](ClO4)2 (3), were obtained from self-assembly of AgX (X = NO3−, BF4−, or ClO4−) with a new flexible double betaine L1 (L1
= 1,3-bis(pyridinio-4-carboxylato)propane). Single crystal X-ray diffraction studies for complexes 1–3 reveal layered open network structures containing novel cavities and channels. Complex 1 consists of an unprecedented rhombic tetrameric Ag4O2
subunit, in which a μ3-η1 coordination mode of the carboxylate group is found for the first time among silver(I) carboxylates. Complex 2 is constructed from a bis(carboxylate-O,O′)-bridged centrosymmetric dimeric subunit, in which the coordination sphere of each silver(I) atom is completed by a monodentate carboxylate group at each axial site. In complex 3, the [Ag2(carboxylate-O,O′)2] dimeric subunits are extended into a polymeric chain through the linkage of each metal centre to carboxylate groups of an adjacent dimer, and such infinite chains are extended into a plane wave-like layer structure by the cross-linkage of the molecular skeletons of the flexible double betaine ligands.
![Bis[2-((oxo)diphenylphosphino)phenyl] ether](http://img.cochemist.com/ccimg/808200/808142-23-6.png)
![Bis[2-((oxo)diphenylphosphino)phenyl] ether](http://img.cochemist.com/ccimg/808200/808142-23-6_b.png)
