Inorganic Chemistry Communications (v.11, #10)

Contents List (iii-xvii).

A novel 2D cobalt(II)-organic framework, [Co2(μ 2-H2O)(hfipbb)2(py)3] · 2(py)] n (1) (H2hfipbb = 4,4′-(hexafluoroisopropylidene)bis(benzoic acid), py = pyridine), has been synthesized under hydrothermal reaction. Single-crystal X-ray diffraction revealed that 1 is a noninterpenetration (4,4) network based on unique tetranuclear clusters and double stranded organic linkers.A novel 2D cobalt(II)-organic framework, [Co2(μ 2-H2O)(hfipbb)2(py)3] · 2(py)] n (1) (H2hfipbb = 4,4′-(hexafluoroisopropylidene)bis(benzoic acid), py = pyridine), has been synthesized under hydrothermal reaction. Single-crystal X-ray diffraction revealed that 1 is a noninterpenetration (4,4) network based on unique tetranuclear clusters and double stranded organic linkers. The powder X-ray diffraction and thermogravimetric analysis of 1 have also been investigated.
Keywords: Metal-organic frameworks; Cobalt(II); Tetranuclear clusters; 4,4′-(Hexafluoroisopropylidene)bis(benzoic acid);

Syntheses, structures and fluorescence studies of two new cadmium(II) pyridyl-diphosphonates by Jiyong Hu; Jin’an Zhao; Hongwei Hou; Yaoting Fan (1110-1112).
Two new cadmium diphosphonate complexes, namely, Cd2(H2O)2[(C5H5N)CH2C(OH)(PO3)(PO3H)]2 1 and Cd2(H2O)(Cl)[(C5H5N)CH2C(OH)(PO3)2] 2, based on [1-hydroxy-2-(3-pyridyl)-ethylidene]-bis-[phosphonic acid] monosodium salt have been synthesized under hydrothermal reaction. The two complexes both show strong fluorescence emission in contrast to the free ligand, respectively, in solid state at ambient temperature.Two new cadmium diphosphonate complexes, namely, Cd2(H2O)2[(C5H5N)CH2C(OH)(PO3)(PO3H)]2 1 and Cd2(H2O)(Cl)[(C5H5N)CH2C(OH)(PO3)2] 2, based on [1-hydroxy-2-(3-pyridyl)-ethylidene]-bis-[phosphonic acid] monosodium salt have been synthesized under hydrothermal reaction and characterized by single crystal X-ray diffraction. Both complexes show strong fluorescence emission in contrast to the free ligand, respectively, in solid state at ambient temperature.
Keywords: Pyridyl-diphosphonate; Cadmium complex; Crystal structure; Luminescence;

Novel metal-free (8, 9), magnesium and zinc porphyrazines (6, 7, 10, 11) containing four peripheral tetraza-dithiahexaoxa cyclindrical or spherical cryptands units have been prepared by tricyclotetramerization reactions using supercryptand 4 or 5.Novel metal-free (8, 9), magnesium and zinc porphyrazines (6, 7, 10, 11) containing four peripheral tetraza-dithiahexaoxa cyclindrical or spherical cryptand units have been prepared by tricyclotetramerization reactions using supercryptand 4 or 5. All new products have been characterized by a combination of mass, elemental analyses, electronic absorption, FT-IR, 1H and 13C NMR spectroscopy.
Keywords: Tetraazaporphyrin; Porphyrazines; Cryptands; Magnesium; Zinc;

A novel 3D 4d–4f heterometallic coordination polymer: Synthesis, crystal structure and luminescence by Ya-Guang Sun; Xiao-Mei Yan; Fu Ding; En-Jun Gao; Wan-Zhong Zhang; Francis Verpoort (1117-1120).
A novel 4d–4f coordination polymer [EuAg(imdc)2] n (1) (imdc = imidazoledicarboxylate) has been hydrothermally synthesized. X-ray single-crystal structural analyses reveal that 1 is three-dimensional framework constructed from one-dimensional chain. 1 also displayed photoluminescent properties in the red range at room temperature.A novel 4d–4f heterometallic coordination polymer [EuAg(imdc)2] n (1) (imdc = imidazoledicarboxylate) has been hydrothermally synthesized and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. X-ray single-crystal structural analysis reveals that 1 is a three-dimensional framework. Furthermore, 1 also displayed photoluminescent properties in the red range at room temperature.
Keywords: Coordination polymers; Heterometallic; Luminescence; Crystal structure;

Triorganoantimony(V) complex (C5H5FeC5H4C(CH3)=NO)2SbPh3 (1) has been prepared by the reaction of Ph3SbCl2 with acetylferroceneoxime C5H5FeC5H4C(CH3)=NOH (2) in 1:2 molar ratio in anhydrous toluene. The complexes have been characterized by elemental analyses, IR and NMR (1H and 13C) spectroscopic studies, and biologic activity was measured. And crystal structures of 1, 2 are reported.Triorganoantimony(V) complex (C5H5FeC5H4C(CH3)=NO)2SbPh3 (1) has been prepared by the reaction of Ph3SbCl2 with acetylferroceneoxime C5H5FeC5H4C(CH3)=NOH (2) in 1:2 molar ratio in anhydrous toluene. The complexes have been characterized by elemental analyses, IR and NMR (1H and 13C) spectroscopic studies, and biologic activity was measured. And crystal structures of 1, 2 were reported. The coordination geometry around the antimony atom in 1 was slightly distorted trigonal bipyramidal with the carbon atoms of the SbPh3 unit in equatorial positions and the two oxygen atoms of the oxime group occupying axial positions. The free oxime was clearly hydrogen bonded (H–N 2.10 Å/2.04 Å in 2) to essentially form a dimer.
Keywords: Organoantimony(V)oximates; Oxime; Thermogravimetric analysis; Antitumor activity; Crystal structure;

Mechanochemical synthesis of the [Al13O4(OH)24(H2O)12]7+ Keggin ion by Peter Billik; Branislav Horváth (1125-1127).
The polymeric [Al13O4(OH)24(H2O)12]7+ Keggin ion has been prepared by mechanochemical reaction between [Al(H2O)6]Cl3 and (NH4)2CO3 reactants.In this study, we demonstrate the synthesis of the [Al13O4(OH)24(H2O)12]7+ Keggin ε-Al13 ion by a mechanochemical reaction between [Al(H2O)6]Cl3 and (NH4)2CO3 reactants. Five grams of the starting mixture corresponding to a molar ratio of (NH4)2CO3/[Al(H2O)6]Cl3  = 0.45:2, 1:2, 1.5:2, 2:2, 2.25:2, 2.55:2 and 3:2 was milled for 5 min. The existence of ε-Al13 was observed at molar ratios of (NH4)2CO3/[Al(H2O)6]Cl3  = 2:2 and higher. Our results show that more than 50% mass of Al from a starting [Al(H2O)6]Cl3 was bonded to the polymeric [Al13O4(OH)24(H2O)12]7+ ionic form at a molar ratio of 2.55:2.
Keywords: Mechanochemical synthesis; ε-Al13 Keggin ion; 27Al NMR; High energy milling;

Macrocyclic silver and gold complexes, [Ag2(L)2](PF6)2 and [Au2(L)2](PF6)2 (L = 1,4-di(N-methylimidazolylidenyl)but-2-yne), have been prepared and structurally characterized.Silver and gold complexes, [Ag2(L)2](PF6)2 and [Au2(L)2](PF6)2, supported by but-2-yne-1,4-diyl linked bis(N-heterocyclic carbene) ligand have been prepared and structurally characterized. The complexes display novel twisted macrocyclic conformation and weak intramolecular metal–metal interaction. The complexes are intensely emissive in their solid states.
Keywords: Silver; Gold; N-Heterocyclic carbene; Luminescence;

Assembly of a new Wells–Dawson polyoxometalate-templated compound based on Fe-btb complex by Aixiang Tian; Jun Ying; Jun Peng; Jingquan Sha; Dongxia Zhu; Haijun Pang; Pengpeng Zhang; Yuan Chen; Min Zhu (1132-1135).
Compound 1 presents an interesting zigzag chain [ Fe ( btb ) ] ∞ 3 + through using bi-dentate “bridging” btb ligands, while the mono-dentate pendant btb molecules act as arms “hugging” the polyanion templates.A new Wells–Dawson polyoxometalate-templated compound, (H3btb)[Fe(btb)3(P2W18O62)] · 4H2O (1) (btb = 1,4-bis(1,2,4-triazol-1-y1)butane), was synthesized under hydrothermal conditions. Compound 1 presents an interesting zigzag chain [ Fe ( btb ) ] ∞ 3 + through using bi-dentate “bridging” btb ligands, while the mono-dentate pendant btb molecules act as arms “hugging” the polyanion templates.
Keywords: Wells–Dawson polyoxometalate; Flexible ligand; Hydrothermal synthesis; Bis(triazole) ligand;

Two copper–organic frameworks, namely, Cu2(CN)(pyzca) (1) and Cu I ( SCN ) Cu 0.5 II ( pyzca ) (2), have been isolated from the reaction of CuX (X = CN, SCN) with Cu(pyzca)2 (pyzca = pyrazine-2-carboxylate) under solvothermal conditions, respectively. They are both characterized by infrared spectroscopy, elemental analysis and X-ray single-crystal analysis. The framework of 1 exhibits an unreported (728)2(7383) network for the (3, 4)-connected nets, while that of 2 can be attributed to the ins topology.The solvothermal reactions of CuX (X = CN, SCN) with Cu(pyzca)2 (pyzca = pyrazine-2-carboxylate) afforded compounds Cu2(CN)(pyzca) (1) and Cu I ( SCN ) Cu 0.5 II ( pyzca ) (2), respectively. They are both characterized by infrared spectroscopy, elemental analysis and X-ray single-crystal analysis. The structure of 1 exhibits a (728)2(7383) network which has not been reported for the (3, 4)-connected nets, while that of 2 displays a (63)(658) network which belongs to the ins topology.
Keywords: Coordination polymers; Solvothermal synthesis; Cyanide-bridging; Triply-bridged SCN ligand; Topology analyses;

A new polymeric inorganic–organic hybrid compound, (NH4)2[Cu2(NH3CH2CH2COO)4(V10O28)] · 10H2O, (1) has been synthesized. The structure of the compound consists of Cu 2 ( NH 3 CH 2 CH 2 COO ) 4 4 + moieties which are connected by bridging V 10 O 28 6 − ions into polymeric chain.A new polymeric inorganic–organic hybrid compound, (NH4)2[Cu2(NH3CH2CH2COO)4(V10O28)] · 10H2O, (1) has been synthesized and characterized by IR, electron and EPR spectroscopy. The thermal decomposition of 1 is briefly described. The structure of 1 consists of Cu 2 ( NH 3 CH 2 CH 2 COO ) 4 4 + moieties which are connected by bridging V 10 O 28 6 − ions into polymeric chain. The charge of polymeric chain is neutralized by ammonium cations. The complex 1 is so far the second known compound in which a decavanadate ion (H x V10O28 (6− x )−) behaves as ligand. The bonding of V 10 O 28 6 − ion to the transition metal complex via end-bonded oxygen atom represents a coordination mode, not yet observed.
Keywords: Decavanadate; Bridging ligand; Polymeric chain; Copper complex; Crystal structure;

Ionothermal reaction in an ionic liquid 1-ethyl-3-methylimidazolium bromide ([emim]Br) yielded a novel two-dimensional metal organic framework, [emim]2[Cd2(btec)Br2] (1) (btec = 1,2,4,5-benzenetetracarboxylate), in which both cation and anion of the ionic liquid are incorporated into the resulting structure.A novel metal organic framework, namely, [emim]2[Cd2(btec)Br2] (1) (emim = 1-ethyl-3-methylimidazolium, btec = 1,2,4,5-benzenetetracarboxylate), was synthesized in an ionothermal reaction by using an ionic liquid 1-ethyl-3-methylimidazolium bromide as solvent and template. Single-crystal X-ray diffraction reveals that the structure features an anionic two-dimensional framework with novel coordination mode of btec ligand. The imidazolium cation emim+ of the ionic liquid acting as charge compensating agent intercalated into the [ Cd 2 ( btec ) Br 2 ] n 2 n - interlayers.
Keywords: Ionic liquid; Ionothermal; Metal-organic framework; Imidazolium bromide; C–H⋯O H-bond;

A novel three-dimensional organic–inorganic hybrid solid [Zn3(3atrz)2(H2O)2(MoO4)2] n (1) (3atrz = 3-amino-1,2,4-triazole) was prepared under hydrothermal condition and characterized by X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction (XRPD), FT-IR, Raman spectrum, TGA and photoluminescence measurements.A novel three-dimensional organic–inorganic hybrid solid [Zn3(3atrz)2(H2O)2(MoO4)2] n (1) (3atrz = 3-amino-1,2,4-triazole) constructed from two-dimensional Mo–O–Zn bimetallic oxide networks was prepared under hydrothermal condition and characterized. Unprecedented {Zn6Mo6} 12 metal central-membered inorganic rings together with novel {Zn6(3atrz)6} metal–organic coordination rings exist in this structure.
Keywords: Zinc; 3-Amino-1,2,4-triazole; Mo/O/M′/ligand hybrid family; Luminescence;

Three unusual 3D 4d–4f coordination polymer, LnAg(ox)(2-pzc)2·H2O [Ln = Eu (1); Tb (2); Dy (3)] [ox = oxalate, 2-pzc = pyrazine-2-carboxylate] has been hydrothermal synthesized and characterized. All three structures exhibit same unusual 3D nanoporous heterometallic coordination frameworks constructed by helical lanthanide–oxalate chains and Ag(2-pzc)2 units. They represent the first examples of 3D 4d–4f heterometallic open coordination frameworks by spontaneous assembly.The self-assembly of pyrazine-2-carboxylate and oxalate with mixed-metal salts under hydrothermal conditions gave three isostructural 3D 4d-4f coordination polymers, LnAg(ox)(2-pzc)2  · H2O [Ln = Eu (1); Tb (2); Dy (3)] [ox = oxalate, 2-pzc = pyrazine-2-carboxylate]. All three structures exhibit same unusual 3D nanoporous heterometallic coordination frameworks constructed by zigzag lanthanide–oxalate chains and Ag(2-pzc)2 units. Furthermore, the luminescent properties of complexes 1 and 2 are discussed.
Keywords: Hydrothermal synthesis; Pyrazine-2-carboxylate; Isostructures; Ln–Ag heterometallic complexes; Luminescence;

This work describes the hydrothermal syntheses and characterizations of two novel coordination polymers [Cd( L )2(p-BDC)] · 2H2O (1) and [Co( L )(BTCA)0.5] (2), in which L is a novel bis(imidazole) ligand, 1,1′-(2,2′-oxybis(ethane-2,1-diyl))bis(1H-imidazole). The topology analyses for these compounds and the luminescent property for 1 are discussed.Two novel coordination polymers containing Cd(II) and Co(II) metals, connected via 1,1′-(2,2′-oxybis(ethane-2,1-diyl))bis(1H-imidazole) ( L ) ligand, have been synthesized. Compound [Cd( L )2(p-BDC)] · 2H2O (1) (p-BDC = 1,4-benzenedicarboxylate anion) is a three-dimensional interdigitated supramolecular architecture. Compound [Co( L )(BTCA)0.5] (2) (BTCA = 1,2,3,4-butanetetracarboxylate anion) possesses a unique (3,4)-connected 3D framework with (83)2(85  · 10) topology.
Keywords: Cadmium; Cobalt; Hydrothermal reaction; Coordination polymers;

Copper–cobalt heterobimetallic ceramic oxide thin film deposition: Synthesis, characterization and application of precursor by Mazhar Hamid; Asif Ali Tahir; Muhammad Mazhar; Kieran C. Molloy; Gabriele Kociok-Köhn (1159-1161).
Thin film of crystalline Cu0.75Co2.25O4 and CuO with particle size range 0.287–0.456 μm was deposited on glass substrate from heterobimetallic precursor, Co4(THF)4(TFA)8(μ-OH)2Cu2(dmae)2  · 0.5C7H8 for technological applications.Thin films of halide free Cu–Co mixed metal oxide have been prepared at 390 °C from the heterobimetallic complex Co4(THF)4(TFA)8(μ-OH)2Cu2(dmae)2  · 0.5C7H8 (1) [dmae =  N,N-dimethylaminoethanol ((CH3)2NCH2CH2O), TFA = triflouroacetate (CF3COO), THF = tetrahydrofurane (C4H8O)] which was prepared by the reaction of [Cu(dmae)Cl]4 and Co(TFA)2  · 4H2O. The precursor was characterized for its melting point, elemental composition, FTIR and X-ray single crystal structure determination. Thin films grown on glass substrate by using AACVD out of complex 1 were characterized by XRD and SEM. TGA and AACVD experiments reveal it to be a suitable precursor for the deposition of halide free Cu–Co mixed-metal oxide thin films at relatively low temperatures.
Keywords: Bimetallic cage; Copper cobalt oxide; CVD precursor; Mixed ceramic oxide;

Two new triazole-bridging 3D supramolecular architectures [Cd(H2O)2(Httr)2](SiF6) (1), [Zn(ttr)(OAc)] (2) (Httr = 3-amino-1H-1,2,4-triazole), are based on 3D layered frameworks. The fluorescent properties of compounds 1 and 2 show the effect of the metals and the substituted groups on luminescent behaviors.Two new triazole-bridging d10 2D layered frameworks, [Cd(H2O)2(Httr)2](SiF6) (1), [Zn(ttr)(OAc)] (2) (Httr = 3-amino-1H-1,2,4-triazole), were synthesized with structures and fluorescence characterized. 1 is based on a kind of 16-membered ring with μ2-1 κN:4 κN coordination mode of Httr and 2 is constructed from the fuse of different 6- and 16-membered rings with μ3-1 κN:2 κN:4 κN mode of ttr. The hydrogen bondings in 1 and 2 between the anions and ttr connect the 2D layers into 3D supramolecular architectures. The fluorescent studies of compounds 1 and 2 show an important difference, emission at 460 nm in 1 and a dual one at 334 and 462 nm in 2.
Keywords: Crystal structure; Fluorescence; 1,2,4-triazole;

Two novel compartmental macrocyclic dinuclear copper(II) complexes with different bridging ligands, formulated as [ Cu 2 II ( L ) ( μ 2 -Cl ) ] · 1.5 ( H 2 O ) (1) and [ Cu 2 II ( L ) ( μ 2 -OAc ) ] · ( DMF ) (2), are characterized by X-ray single-crystal diffraction. Due to the use of different bridges and bulky t-bu groups, different molecular conformation and dimeric packing structures are observed.Two novel compartmental macrocyclic dinuclear copper(II) complexes with different bridging ligands, formulated as [ Cu 2 II ( L ) ( μ 2 -Cl ) ] · 1.5 ( H 2 O ) (1) and [ Cu 2 II ( L ) ( μ 2 -OAc ) ] · ( DMF ) (2), are characterized by X-ray single-crystal diffraction where LH3 is a pentadentate ligand obtained from the Schiff base condensation between 3,5-di-tert-butyl-2-hydroxybenzaldehyde and 2,6-bis(aminomethyl)-4-chlorophenol in a molar ratio of 2:1. Due to the use of different bridges and bulky t-bu groups, different molecular conformation and dimeric packing structures are observed.
Keywords: Dinuclear copper(II) complex; Macrocyclic compounds; Schiff base; Structural elucidation;

Facile N–N coupling and copper (II) promoted cleavage of N,N′-linked N-methylbenzimidazole by Doo Hwan Jeong; Won Jin Park; Jong Hwa Jeong; David G. Churchill; Hyosun Lee (1170-1173).
The easy and high yielding, yet non-trivial formation of N,N′-linked NHC ligands, which is an uncommon phenomenon during the desired synthetic NHC reaction protocols, specifically, the N,N′-linked NHCs are 3,3-dimethyl-1,1-bibenzimidazolium dichloride (2a) and 3,3-dibenzyl-1,1-bibenzimidazolium dichloride (2b), were formed. Furthermore, the compound (2a) was homolytically cleaved by CuO or CuCl2 under NaH to furnish the binuclear species [(N-MeBenzimz)2Cu(μ-Cl)]2Cl2 (Ia) characterized by single crystal X-ray crystallography.Together with the facile and high yielding formation of N,N′-linked NHC ligand, the complexation of N-methylbenzimidazole (1a), N-methylbenzimdiazolium chloride (4a) and N,N′-linked NHC ligand, 3,3-dimethyl-1,1-bibenzimidazolium dichloride (2a), with CuO or CuCl2 give a dichloro-bridged binuclear copper(II) species (Ia), as characterized by IR spectroscopy and X-ray.
Keywords: N-heterocyclic carbenes (NHCs); Benzimidazole; N-alkylbenzimidazole; N,N′-linked NHC;

trans-Disubstituted diamido/diamine cyclam zirconium complexes by Rui F. Munhá; Luís G. Alves; Nuno Maulide; M. Teresa Duarte; István E. Markó; Michael D. Fryzuk; Ana M. Martins (1174-1176).
trans-N,N-CH2PhR2Cyclam derivatives (PhR2  = C6H5; 3,5-Me2C6H3; 3,5-tBu2C6H3) and its lithium and zirconium complexes are reported. Zirconium compounds were tested as ε-caprolactone and ethylene polymerisation catalysts.The reaction of H2[1,8-dibenzyl-1,4,8,11-tetraazacyclotetradecane] (H2Bn2Cyclam) with 2 equiv of LiBu gives Li2Bn2Cyclam(L)2 (L = Et2O or THF) that reacts with ZrCl4(THF)2 to afford (Bn2Cyclam)ZrCl2 in 40% yield. Alternatively (Bn2Cyclam)ZrCl2 may be obtained via ZrCl2(CH2SiMe3)2(Et2O)2 in a significantly higher yield (87%), avoiding the lithiation of H2Bn2Cyclam. The syntheses of other H2 Bn2Cyclam ligand precursors (Bn = 3,5-dimethylbenzyl and 3,5-di(tert-butyl)benzyl) and the corresponding Zr derivatives ({3,5-Me2Bn}2-Cyclam)ZrCl2 and ({3,5-tBu2Bn}2-Cyclam)ZrCl2 are also reported. Results on preliminary tests of ε-caprolactone and ethylene polymerisation reactions are presented.
Keywords: Zirconium; Cyclam; Tetraazamacrocycles; Amido ligands; Ethylene polymerisation; ε-Caprolactone polymerisation;

The mixed-valence trinuclear cobalt compound {[Co(CN)3(tBuNC)2](μ-CN)[Co(tBuNC)4] (μ-CN)[Co(CN)3(tBuNC)2]} is produced from the reaction of CoCl2, KCN and tert-butylisocyanide. In the resulting structure, three octahedrally coordinated cobalt atoms are present with two cobalt atoms formally showing the oxidation state +III, whereas the central cobalt still exhibits the formal oxidation state +II.The mixed-valence trinuclear cobalt compound {[Co(CN)3(tBuNC)2](μ-CN)[Co(tBuNC)4](μ-CN)[Co(CN)3(tBuNC)2]} is produced from the reaction of CoCl2 with KCN and tert-butylisocyanide. In the resulting structure two cobalt atoms formally show the oxidation state +III, whereas the central cobalt still exhibits the formal oxidation state +II. All cobalt atoms are octahedrally coordinated by cyanide and isocyanide ligands. The supramolecular structure is determined by C–H⋯O and C–H⋯N hydrogen bonds linking acetone molecules to the trimeric complex as well as connecting the complex units into infinite chains.
Keywords: Cobalt; Mixed-valence; Cyanide; Isocyanide; X-ray;

A metal–organic framework containing meso-helical chains: Synthesis, characterization and luminescent property by Kother Osman Ashiry; Ya-Hui Zhao; Kui-Zhan Shao; Zhong-Min Su; Yao-Mei Fu; Xiang-Rong Hao (1181-1183).
The metal–organic framework (MOF), [Cd3(pmb)2(bpdc)2] · 2H2O (1), has been hydrothermally synthesized and structurally characterized. The infinite wave-like 1D metal–oxygen chains made by Cd3N4O12 clusters in 1 construct a 2D framework bridged by the carboxylate of bpdc ligand, in which interesting meso-helical chains are constructed by metal centers and pmb ligands along the c-axis.A new metal–organic frameworks (MOFs), [Cd3(pmb)2(bpdc)2] 2H2O (1) (pmb = 3,5-bis(4-pyridylmethylenoxyl)benzoate, bpdc = 2,2′-biphenyldicarboxylate), has been synthesized by hydrothermal method and structurally characterized through IR, TG and single-crystal X-ray analysis. The infinite wave-like 1D metal–oxygen chains made by Cd3N4O12 clusters in 1 bridged by the carboxylate of bpdc ligand, construct a 2D framework in which interesting meso-helical chains are constructed by metal centers and pmb ligands. Solid state luminescent spectrum of 1 also has been investigated at room temperature.
Keywords: Bridging ligand; Hydrothermal method; Coordination polymer; X-ray diffraction; Fluorescence;

The novel tungstoantimonate [Sb2W20(OH)2(dmso)2O66]8− was isolated as [Ru(bpy)3]2+ salts by the reaction of [Sb2W20Ni2(H2O)6O70]10− and [Ru(bpy)3]2+ in dmso/H2O media followed the loss of Ni2(H2O)6 unit and the coordination of dmso groups, and it exhibits two highly unusual W–(dmso) bonds in polyoxoanions.A novel dmso-coordinated heteropolytungstate [Sb2W20(OH)2(dmso)2O66]8− (1) has been successfully isolated as [Ru(bpy)3]2+ salts by routine synthetic reaction in mixed solutions with dmso and water. The compound was characterized by spectroscopic methods as well as by X-ray single crystal structure analysis. The compound represents a tungstoantimonate framework with two W–O–S(CH3)2 bonds.
Keywords: dmso; Antimony(III); Polyoxometalate; Tungsten; Crystal structure;

[Tb{Tb4(hpmba)83-ΟΗ)44-ΟΗ)}2OH] (hpmba = 2-hydroxy-N-((pyridin-2-yl)methyl)benzamide) was prepared and its structures was determined by X-ray crystallography, which exhibits a novel “sandglass”-like nonanuclear structure. The ITO/PVK/complex/Al OLED with this compound as light-emitting material has a maximum electroluminescence intensity when the driving voltages were increased to 11 V.The synthesis, crystal structure and photophysical properties of [Tb{Tb4(hpmba)83-ΟΗ)44-ΟΗ)}2OH] (hpmba = 2-hydroxy-N-((pyridin-2-yl)methyl)benzamide) was presented. The crystal structure exhibits a novel sandglass-like nonanuclear structure. The complex is strongly emissive with the lifetime about 1.02 ms at 546 nm in CH3CN at 298 K. The ITO/PVK/complex/Al OLED with the compound as a light-emitting material has also been fabricated; it has a maximum electroluminescence intensity when the driving voltages were increased to 11 V.
Keywords: 2-hydroxy-N-((pyridin-2-yl) methyl) benzamide; Sandglass; Terbium; OLED;

[Zn4(BTC)24-O)(H2O)2] was synthesized from ionothermal synthesis with Zn(NO3)2  · 6H2O and H3BTC ligand (H3BTC = 1,3,5-benzenetricarboxylic acid) in 1-ethyl-3-methylimidazolium bromide ionic liquid as a solvent. The compound features 3-D structures with channels constructed from distorted [Zn44-O)] subunits linking with BTC3−.A zinc metal-organic framework (MOF), [Zn4(BTC)24-O)(H2O)2], was synthesized with Zn(NO3)2  · 6H2O and H3BTC ligand (H3BTC = 1,3,5-benzenetricarboxylic acid) by ionothermal synthesis in 1-ethyl-3-methylimidazolium bromide ionic liquid as solvent. The compound features a 3-D architecture constructed by linking [Zn44-O)] subunits with BTC3− ligands. They are composed of two five-coordinated and two four-coordinated Zn ions, different from the [Zn44-O)] units of other MOFs. The effect of reaction conditions to the MOF structure is discussed.
Keywords: Ionothermal synthesis; Zinc; 1,3,5-Benzenetricarboxylic acid; MOF; [Zn44-O)] subunit;

Novel trinuclear oxo-centred [ Co 3 III O ( O 2 CPh ) 3 ( pyCHNO ) 3 ] + complexes and the mixed-valence ‘bent’ trinuclear [ Co 2 III CoII ( OH ) Cl 3 ( pyCHNO ) 4 ] complex bearing dinuclear [ Co 2 III ( μ 2 -OH ) ( pyCHNO ) 4 ] and tetrahedral [ Co II Cl 3 ] ‘inorganic’ units bridged by an oximato oxygen atom of the ligand have been synthesized and characterized.The use of 2-pyridyl aldoxime (pyCHNOH) in cobalt carboxylate chemistry has yielded compounds 2 [ Co 3 III O ( O 2 CPh ) 3 ( pyCHNO ) 3 ] [ Co 3 II ( O 2 CPh ) 8 ] · 7.67 MeCN ( 1 · 7.67 MeCN ) and [ Co 3 III O ( O 2 CPh ) 3 ( pyCHNO ) 3 ] ( PhCO 2 ) · 0.5 PhCO 2 H · 2 MeCN ( 2 · 0.5 PhCO 2 H · 2 MeCN ) in mixture, as well as compounds 2 [ Co 3 III O ( O 2 CPh ) 3 ( pyCHNO ) 3 ] ( PhCO 2 ) ( NO 3 ) · ( PhCO 2 H ) · H 2 O ( 3 · PhCO 2 H · H 2 O ) and [ Co 2 III Co II ( OH ) Cl 3 ( pyCHNO ) 4 ] · 0 · 5 MeCN · 0.5 H 2 O ( 4 · 0.5 MeCN · 0.5 H 2 O ) . Complexes 13 have been isolated from the 1:1:2 CoX 2 ( X = Cl - , NO 3 - ) / pyCHNOH / PhCO 2 Na molar ratio reactions in MeCN, whereas the 1:1:1 CoX2(X = Cl)/pyCHNOH/PhCO2Na molar ratio reaction in MeCN afforded complex 4. Compounds 13 contain the cation [ Co 3 III O ( O 2 CPh ) 3 ( pyCHNO ) 3 ] + representing the first triangular oxo-centred CoIII cluster with pyCHNO, whereas compound 4 displays an unusual structural motif consisting of dinuclear [ Co 2 III ( μ 2 -OH ) ( pyCHNO ) 4 ] + and tetrahedral [CoIICl3] units bridged by an oximato oxygen atom of the ligand.
Keywords: Cobalt complexes; Oxo-centred complexes; Mixed-valence complexes; 2-Pyridyl aldoxime; Crystal structures;

1H NMR, 13C NMR, and EPR studies have revealed that bis(benzaldehyde) complex of highly ruffled iron(III) porphyrinate adopts the purest S  = 3/2(d xy ) electronic ground state among the intermediate-spin complexes reported previously.Analysis of the 1H and 13C NMR chemical shifts has revealed that bis-ligated iron(III) porphyrinates, [Fe(Porphyrin)(L)2]±, adopt the ( d xz , d yz ) 3 ( d xy ) 1 ( d z 2 ) 1 ground state if the complex has highly ruffled porphyrin core and carries weak oxygen ligand with multiple bond such as benzaldehyde.
Keywords: Iron(III); Porphyrin complexes; Spin state; Intermediate-spin; Electron configuration;

The room-temperature reaction of [7-Me3N-nido-7-CB10H12] (1) with [(η4-C10H12)2Rh2(μ-Cl)2] (2) in C6H6–EtOH mixture in the presence of Proton Sponge affords two isomeric agostic monocarbon (η-dicyclopentenyl)-closo-rhodacarborane complexes, differing in hapticity of the carbocyclic ligand, viz. [2,2-{(2’,3’-η2):(5-η1)-C10H13}-1-(Me3N)-2,1-closo-RhCB10H10] (3) and [2-{(1’-3’-η3)-C10H13}-1-(Me3N)-2,1-closo-RhCB10H10] (4). Both complexes were characterized by a combination of NMR and IR spectroscopy as well as by single-crystal X-ray diffraction studies.The [7-Me3N-nido-7-CB10H12] (1), after being treated with two molar equiv. of Proton Sponge, reacts with [(η4-C10H12)2Rh2(μ-Cl)2] (2) in benzene–ethanol solution affording two isomeric monocarbon (η-dicyclopentenyl)-closo-rhodacarborane complexes, differing in hapticity of the carbocyclic ligand, viz. [2,2-{(2′,3′-η2):(5′-η1)-C10H13}-1-(Me3N)-2,1-closo-RhCB10H10] (3) and [2-{(1′-3′-η3)-C10H13}-1-(Me3N)-2,1-closo-RhCB10H10] (4). Isomeric compounds 3 and 4 were characterized by analytical, multinuclear NMR spectroscopic data as well as by single-crystal X-ray diffraction study, which revealed the existence of an agostic C–H⋯Rh interaction in both the species.
Keywords: Monocarbon closo-rhodacarboranes; Structural isomers; Agostic C–H⋯Rh interaction; Crystal structures; NMR spectroscopy;

The hydrothermal reaction of MoO3, CuSO4  · 5H2O, terpyridine and bis-N,N-(methylphosphonic acid) gave crystals of a three-dimensional bimetallic oxide [{Cu(terpy)}2Mo6O17(H2O)(O3PCH2NH2CH2PO3)2] · H2O, constructed from the unusual {Mo6O17(H2O)(O3PCH2NH2CH2PO3)2}4− clusters linked through {Cu(terpy)}2+ subunits.The hydrothermal reaction of MoO3, CuSO4  · 5H2O, 2,2′:6′:2″-terpyridine (terpy) and bis-N,N-(methylphosphonic acid) amine (H2O3PCH2NHCH2PO3H2) provided blue crystals of the bimetallic oxide [{Cu(terpy)}2Mo6O17(H2O)(O3PCH2NH2CH2PO3)2] · H2O (1  · H2O). The three-dimensional structure of 1 is constructed from {Mo6O17(H2O)(O3PCH2NH2CH2PO3)2}4− clusters linked through {Cu(terpy)}2+ subunits. The cluster consists of three pairs of edge-sharing {MoO6} octahedra linked through corner-sharing interactions into a {Mo6O6} ring. One phosphonate ligand spans the diameter of the ring, bridging four molybdenum sites and leaving at a pendant {P=O} group at each terminus. The second diphosphonate ligand exploits one {–PO3} unit to cap the hexamolybdate ring and bridge all six molybdenum sites while the second {–PO3} terminus bridges two molybdenum sites, leaving a pendant {P=O} unit. Crystal data: C34H45Cu2Mo6N8O35P4: monoclinic, P21/n, a  = 11.9431(7) Å, b  = 17.382(1) Å, c  = 27.524(2) Å, β  = 90.429(1)°, V  = 5713.7(6) Å3, Z  = 4, D calc  = 2.270 g cm−3, R 1  = 0.0466.
Keywords: Organic–inorganic frameworks; Bimetallic oxides; Molybdophosphonate clusters;

Direct template synthesis of a heterometallic CoIII/ZnII complex: The advantage of using a metal powder as a starting material by Denys V. Shevchenko; Vladimir N. Kokozay; Marina V. Krasovska; Oleg V. Shishkin (1209-1211).
The use of elemental cobalt as starting materials allowed us to obtain [Co(L1)Cl2][ZnCl3(DMF)], which cannot be prepared by traditional template synthesis.The heterometallic complex [Co(L1)Cl2][ZnCl3(DMF)] (L1  = 4,6,6-trimethyl-1,9-diamino-3,7-diazanon-3-ene) has been obtained by direct template synthesis from cobalt powder, zinc oxide, zinc chloride, ethylenediamine dihydrochloride and acetone in dimethylformamide and characterized by X-ray crystallographic analysis. The mechanism of the complex formation is suggested.
Keywords: Direct synthesis; Template synthesis; Cobalt; Zinc; Crystal structure;

ZnCl3(4-methyl-4,4′-bipyridinium) with 4-methyl-4,4′-bipyridinium generated in situ: synthesis, structure and photoluminescence by Wen-Tong Chen; Dong-Sheng Liu; Shao-Ming Ying; Hua-Long Chen; Ya-Ping Xu (1212-1214).
A novel viologen-based complex ZnCl3(4-methyl-4,4′-bipyridinium), in which the 4-methyl-4,4′-bipyridinium was generated in situ, has been synthesized via hydrothermal reaction. The crystal structure features an isolated structure, based on a 4-methyl-4,4′-bipyridinium moiety coordinating to a zinc atom that is further terminally bound by three chlorine atoms. The complex exhibits a strong blue fluorescent emission band.A novel viologen(4,4′-bipyridinium)-based complex ZnCl3(4-methyl-4,4′-bipyridinium) (1), in which the 4-methyl-4,4′-bipyridinium (MQ + ) was generated in situ, has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. The title complex features an isolated structure, based on the MQ + ligand coordinating to a zinc atom that is further terminally bound by three chlorine atoms. Photoluminescence investigation reveals a strong emission in blue region, which may originate from π → π charge-transfer interaction of the MQ + ligand.
Keywords: Bipyridine; In situ; Photoluminescence; Viologen; Zinc;

Novel calixarene–Schiff bases that bind silver(I) ion by Bernadette S. Creaven; Mary Deasy; Paul M. Flood; John McGinley; Brian A. Murray (1215-1220).
Two novel calix[4]arene–Schiff base receptors have been synthesized. One of the new compounds has two pendant aldimines, while the second has been prepared by two-point attachment of a calixarene–dialdehyde onto a calixarene–diamine to form a “calix-tube”. Preliminary binding studies with AgClO4 show large complexation-induced shifts in 1H NMR positions.Two novel calix[4]arene–Schiff base receptors have been synthesized. One of the new compounds has two pendant aldimines, while the second has been prepared by two-point attachment of a calixarene–dialdehyde onto a calixarene–diamine to form a “calix-tube”. Preliminary binding studies with AgClO4 show large complexation-induced shifts in 1H NMR positions.
Keywords: Calixarenes; Schiff base; Silver; Complexation;

Zn33-OH)2(2,4-bptc)] n ·2nH2O (1) was synthesized from 2,2′,4,4′-biphenyltetracarboxylic acid (2,4-H4bptc) and Zn(NO3)2  · 6H2O in the presence of NaOH hydrothermally. Crystal structure indicates that 1 is Zn2(OH)2 diamond chains linked through 2,2′,4,4′-biphenyltetracarboxylate. 1 was characterized by TG, IR and fluorescence spectra. 1 is the first example of 2,4-H4bptc complex and also first complex contains Zn2(OH)2 diamond-core chains.Reaction of 2,2′,4,4′-biphenyltetracarboxylic acid (2,4-H4bptc), Zn(NO3)2  · 6H2O in the presence of NaOH hydrothermally at 180 °C affords the first 2,4-H4bptc complex [Zn33-OH)2(2,4-bptc)] n  · 2nH2O (1). Crystal structure indicates that 1 is Zn2(OH)2 diamond-core chains linked through 2,2′,4,4′-biphenyltetracarboxylate. 1 was characterized by TG, IR and fluorescence spectra. 1 is the first example of 2,4-H4bptc complex and also first neat Zn2(OH)2 diamond-core chains.
Keywords: 2,2′,4,4′-Biphenyltetracarboxylic acid; Zn2(OH)2 diamond-core chains; Crystal structure; Hydrothermal synthesis;

Two-dimensional square grid of neutral phosphonate ligands and eight-coordinated metal ions by Xiang-Dong Zhang; Chun-Hua Ge; Xiao-Yan Zhang; Chun-Yue Shi; Cui He; Jing Yin (1224-1226).
A two dimensional cadmium complex has been synthesized and characterized by X-ray crystallography, UV–Vis spectroscopy, luminescent spectroscopy and TG. The metal ion is in a coordination environment of distorted dodecahedron. Neutral phosphonate esters bridge metal ions to form infinite square grid framework. C–H⋯O interactions further link these grid into three dimensional supramolecular structure.Two dimensional coordination polymer [CdL2(NO3)2] n (where L = 4,4′-bis(dimethylphosphonomethyl)biphenyl) has been achieved. The crystal structure and molecular composition are measured using elemental analysis and X-ray crystal structure. Two-dimensional square grid was formed by semi-rigid phosphonate ligands bridge metals, in which the metals adopt rare eight-coordinated geometry. Weak C–H⋯O hydrogen bonds which between coordinated nitrate anion and methyl group of phosphonate ligands link two dimensional grids generating three dimensional supramolecular networks without interpenetration.
Keywords: Phosphonate ligand; C–H⋯O hydrogen bond; Eight-coordinated geometry; Cadmium complex;

Unprecedented cadmium(II) complex with (44  · 66) net topology and in situ ligand synthesis by Zheng-Shuai Bai; Jing Xu; Zhi Su; Wei-Yin Sun (1227-1230).
Two complexes [Cu(2,4-Hpydca)2(H2O)2] (1) and [Cd(2,4-pydca)] n (2) were synthesized by hydrothermal reactions with in situ transformation of 4,4′-bipyridine-2,2′-dicarboxylic acid (H2BPDCA) to pyridine-2,4-dicarboxylic acid (H2pydca), and 2 is the first binodal 5-connecting 3D framework with unprecedented (44  · 66) net topology.Hydrothermal reactions of 4,4′-bipyridine-2,2′-dicarboxylic acid (H2BPDCA) with Cu(II) and Cd(II) nitrate salts result in the formation of two complexes [Cu(2,4-Hpydca)2(H2O)2] (1) and [Cd(2,4-pydca)] n (2) with pyridine-2,4-dicarboxylate (2,4-pydca2−), rather than BPDCA2−, as ligand, namely the in situ transformation of H2BPDCA to H2pydca occurred under the hydrothermal conditions. Complex 1 has been previously reported from different synthetic route, however, complex 2 is the first binodal 5-connecting 3D framework with unprecedented (44  · 66) net topology. The results provide a new strategy for in situ ligand synthesis and construction of coordination polymers with specific topology.
Keywords: Cadmium(II) complex; In situ ligand synthesis; Hydrothermal reaction; Metal–organic framework; TGA analysis;

Polynuclear copper(II) carboxylates with 2,2′-bipyridine or 1,10-phenanthroline: Synthesis, characterization, X-ray structures and magnetism by Jaursup Boonmak; Sujittra Youngme; Thidarat Chotkhun; Chainarong Engkagul; Narongsak Chaichit; Gerard A. van Albada; Jan Reedijk (1231-1235).
The novel polynuclear [Cu2(phen)2(μ-O2CH)2(O2CH)2] n (1) and [Cu6(bpy)6(μ-O2CC2H5)7(H2O)2)](PF6)5  · 2H2O (2) were synthesized and characterized by elemental analyses, electronic and EPR spectra and X-ray structure analyses. Compound 1 consists of four independent zigzag polymeric chains of dinuclear [Cu2(phen)2(μ-O2CH)2(O2CH)2] subunits with the asymmetric bidentate bridging formato groups linking Cu atoms in an antianti configuration. The hexanuclear copper(II) molecule of compound 2 contains three different dinuclear units with the synsyn-μ-η11 and syn–anti312 propionate bridges. Either intra- or intermolecular π–π stacking interactions among aromatic moieties of alpha-diimine chelating didentates remarkably play a key role to stabilize the polynuclear structure of 1 and 2. The magnetic susceptibility measurement (5–350 K) of compound 2 reveals a weak antiferromagnetic interaction between the Cu(II) centers.[Cu2(phen)2(μ-O2CH)2(O2CH)2] n (1) and [Cu6(bpy)6(μ-O2CC2H5)7(H2O)2)](PF6)5  · 2H2O (2) were synthesized and characterized by elemental analyses, electronic and EPR spectra and X-ray structure analyses. Compound 1 consists of four independent polymeric chains of dinuclear [Cu2(phen)2(μ-O2CH)2(O2CH)2] subunits with the asymmetric bidentate bridging formato groups linking Cu atoms in an antianti configuration. All Cu(II) ions are in a distorted square-pyramidal geometry. The hexanuclear copper(II) molecule of compound 2 is constructed from three different dinuclear units connected to each other via two synanti312 carboxylato bridges. All copper(II) ions are in the distorted square-pyramidal geometry. Two terminal dinuclear units are similar in structure in which both Cu(II) ions are doubly bridged by the syn–syn carboxylato anions, while those of the central dinuclear entity are triply bridged by two μ312 carboxylato anions via monoatomic bridging fashion and one syn–syn carboxylato anion. The magnetic susceptibility (5–350 K) of compound 2 was measured and agree with a weak antiferromagnetic interaction between the Cu(II) centers.
Keywords: Copper(II); Crystal structures; EPR; Magnetism; Carboxylato bridges;

A novel mixed-valence vanadium(IV/V) complex containing linear mono-μ-oxo [V3O5]4+ core by Xi-He Huang; Chang-Cang Huang; Xiao-Huan Qin; Lai-Sheng Zhai; Dong-Sheng Liu (1236-1238).
A novel trinuclear VV/IV/V complex, {[VO2(phen)(SO4)(H2O)]2[VO(phen)(H2O)]} (1) was prepared and characterized by single-crystal X-ray diffraction. Complex 1 contains a novel linear mixed valence [V3O5]4+ core structure, which can be considered as a partial delocalized system (i.e. Class II). It represents the first mixed-valence polynuclear vanadium complex with linear mono-μ-oxo-vanadate/vanadyl core.A novel trinuclear VV/IV/V complex, [VO2(phen)(SO4)(H2O)]2[VO(phen)(H2O)]} (1), containing linear mono-μ-oxo [V3O5]4+ core was prepared and characterized by single-crystal X-ray diffraction. Complex 1 represents the first mixed-valence polynuclear vanadium complex with linear mono-μ-oxo-vanadium/vanadyl core. Furthermore, the study of the EPR and electronic spectrum of complex 1 show that it is a Class II species according to the Robin and Day classification scheme.
Keywords: Vanadium complex; Mixed valence; Trinuclear;

Two copper(II) coordination polymers containing atza ligand [atza = 5-aminotetrazole-1-acetato] by Gao-Wen Yang; Qiao-Yun Li; Yi Zhou; Guo-Qing Gu; Yun-Sheng Ma; Rong-Xin Yuan (1239-1242).
Two copper(II) coordination polymers [Cu(atza)2]n  · 2nH2O (1) and [Cu(atza)2(4,4′-bipy)0.5  · H2O]n (2) [atza = 5-aminotetrazole-1-acetato] have been synthesized. Compound 2 is a offspring from reaction of a preformed compound 1 with 4,4′-bipyridyl. The dehydration and rehydration processes of compound 1 were investigated.Two copper(II) coordination polymers [Cu(atza)2]n  · 2nH2O (1) and [Cu(atza)2(4,4′-bipy)0.5  · H2O]n (2) [atza = 5-aminotetrazole-1-acetato] have been synthesized and characterized by X-ray diffraction analysis, element analysis and IR spectra. Compound 2 is a offspring from reaction of a preformed compound 1 with 4,4′-bipyridyl. The two connected modes of the 2D network layered are provided through μ-atza and/or 4,4′-bipyridyl bridges, and forming 3D supramolecular structures by hydrogen bonding interactions. The dehydration and rehydration processes of compound 1 was investigated
Keywords: Copper(II); Crystal structures; 5-aminotetrazole-1-acetic acid; 4,4′-bipyridyl; Rehydration properties;

Compound Co3(hpyedpH)2(H2O)4  · H2O (1) (hpyedpH4  = 1-hydroxy-2-(3-pyridyl)ethylidene-1,1-diphosphonic acid) has a layer structure made up of {CoO6} octahedra and {CPO3} tetrahedra which contains 4-, 8- and 16-membered rings. It is a ferrimagnet with T c  = 3.8 K below which slow magnetic relaxation is observed.Compound Co3(hpyedpH)2(H2O)4  · H2O (1) (hpyedpH4  = 1-hydroxy-2-(3-pyridyl)ethylidene-1,1-diphosphonic acid) has a layer structure where chains of {Co3(hpyedpH)2(H2O)4} n are connected by {CPO3} tetrahedra, generating a layer containing 4-, 8- and 16-membered rings. Magnetic measurements show that compound 1 is a ferrimagnet with T c  = 3.8 K. Slow magnetic relaxation is observed below 3.8 K, possibly due to the domain wall movement.
Keywords: Cobalt; Diphosphonate; Magnetic property; Layer structure; Ferrimagnet; Slow magnetic relaxation;

A novel pentanuclear Zn(II) coordination polymer with double helices: Synthesis, structure and luminescent property by Gang Yuan; Kui-Zhan Shao; Xin-Long Wang; Ya-Qian Lan; Ya-Hui Zhao; Zhong-Min Su (1246-1249).
A novel 3D coordination polymer, [Zn5(hqc)43-OH)2] n (1), has been prepared by hydrothermal reaction. The hqc2− as bridging ligand links pentanuclear Zn(II) cluster to construct a three-dimensional framework. In this framework, there exists an intriguing double helical motif.A novel 3D coordination polymer, [Zn5(hqc)43-OH)2] n (1), has been prepared by hydrothermal reaction and characterized by elemental analyses, TGA, and single-crystal X-ray diffraction analysis. Compound 1 is built by hqc2− ligands bridging pentanuclear Zn(II) SBUs, [Zn53-OH)2], and there is coexistence of left-, and right-handed double helical chains in the 3D network. It represents the first pentanuclear Zn(II) coordination polymers with double helices constructed from quinoline-based carboxylic acid. In addition, the fluorescent property of compound 1 was also determined, which exhibits blue fluorescence at 441 nm in the solid-state upon excitation at 330 nm.
Keywords: Coordination polymer; Double helices; Hydrothermal reaction; 2-Hydroxyquinoline-4-carboxylic acid; d10 Metal;

Rapid synthesis of a novel cadmium imidazole-4,5-dicarboxylate metal–organic framework under microwave-assisted solvothermal condition by Wenlong Liu; Lihua Ye; Xinfang Liu; Limin Yuan; Xiaolong Lu; Jiaxun Jiang (1250-1252).
A novel cadmium organic framework based on 4,5-imidazoledicarboxylic acid in the presence of 1,1’-(1,4-butanediyl)bis(imidazole) has been synthesized rapidly under microwave-assisted solvothermal condition and structurally characterized. The thermal stability and photoluminescence property of 1 are also investigated.A novel three-dimensional (3D) coordination polymer, [Cd(μ3-HIDC)(bbi)0.5] n (1) (H3IDC = 4,5-imidazoledicarboxylic acid, bbi = 1,1’-(1,4-butanediyl)bis(imidazole)), has been synthesized under microwave heating solvothermal conditions and characterized by elemental analysis, IR, TG, and single crystal X-ray diffraction. The crystal structure reveal that compound 1 consists of 2D brickwall-like networks of [Cd(μ3-HIDC)] n , which are further linked through μ2-bbi to generate a 3D structure. Compound 1 is stable up to 330 °C and displays strong blue fluorescent emission at room temperature. This work demonstrates that microwave-assisted solvothermal synthesis method is an efficient and fast way to prepare metal coordination polymers.
Keywords: Solvothermal synthesis; Microwave-assisted; Crystal structure; MOF; Photoluminescence;

A new eight-connected CsCl-type net using bicadmium cores as nodes by Ya-li Yao; Yun-Xia Che; Ji-Min Zheng (1253-1255).
Hydrothermal reactions of benzimidazole-5-carboxylate acid (HL) and cadmium(II) nitrate yielded a novel three-dimensional compound [Cd(L)2] · H2O (1) under base conditions. Complex 1 is the first example of an eight-connected CsCl-type net utilizing bicadmium cores as eight-connected nodes and HL as linkers. And it exhibits blue fluoresent emission band in the solid state.Hydrothermal reactions of benzimidazole-5-carboxylate acid (HL) and cadmium(II) nitrate under base conditions lead to a novel three-dimensional microporous coordination polymer [Cd(L)2] · H2O (1). Topologically, it can be described as an eight-connected CsCl-type net (42464) utilizing bicadmium cores as eight-connected nodes and HL as linkers. A blue fluorescence emission spectrum of compound 1 was observed.
Keywords: Microporous coordination polymer; Cadmium; 8-Connected net; Topology; Fluorescence;

A novel hydroxo-bridged cyclic tetranuclear copper(II) complex with the guanazole ligand (3,5-diamino-1,2,4-triazole = Hdatrz), [Cu4(datrz)42-OH)2(NO3) (H2O)6] · (NO3) · 5(H2O) (1) has considerably short Cu⋯Cu distances in the range of 3.3550(4)–3.3611(4) Å. Thermal analysis of 1 reveals that the cyclic framework constructed with hydroxo and guanazole ligands is stable up to 285 °C.A novel hydroxo-bridged cyclic tetranuclear copper(II) complex with the guanazole ligand (3,5-diamino-1,2,4-triazole = Hdatrz), [Cu4(datrz)42-OH)2(NO3) (H2O)6] · (NO3) · 5(H2O) (1) has been synthesised and characterised by X-ray crystallography. In 1, the four copper(II) centres are linked by hydroxo bridges and the N1,N2-coordination of the deprotonated guanazole ligands. The core has considerably short Cu⋯Cu distances in the range of 3.3550(4)–3.3611(4) Å. Thermal analysis of 1 reveals that the cyclic framework constructed with hydroxo and guanazole ligands is stable up to 285 °C.
Keywords: Cyclic tetranuclear; Hydroxo bridged; Copper(II) complex; Guanazole ligand;

A novel coordination polymer {[Dy2(bpdc)3(H2O)3] · H2O} n has been successfully synthesized through hydrothermal route, which shows unusual mixed-connected network topology as well as high thermal stability and strong fluorescent emission.A novel 3D coordination polymer {[Dy2(bpdc)3(H2O)3] · H2O} n (bpdc = 2,2′-bipyridine-4,4′- dicarboxylate) based on inorganic rod-shaped infinite secondary building unit is presented, which possesses unusual mixed-connected network topology and shows high thermal stability and strong photoluminescence at room temperature.
Keywords: Coordination polymer; Network topology; Thermal stability; Luminescent property;

The first anion template cubic cyanometallate cage and its 3,5-dimethyltris(pyrazolyl)methane iron(II, III) tricyanide building blocks by Chu-Chen Shi; Chi-Shian Chen; Sodio C.N. Hsu; Wen-Yann Yeh; Michael Y. Chiang; Ting-Shen Kuo (1264-1266).
Several 3,5-dimethyltris(pyrazolyl)methane iron(II, III) tricyanide building units have been prepared and characterized. Treatment of K[(HC(3,5-Me2Pz)3)FeII(CN)3](K+ 1 ) with FeII(H2O)6(BF4)2 affords a new anion template cubic cyanometallate cage [(BF4) ⊂ {FeII(H2O)}4{(HC(3,5-Me2Pz)3)FeII(CN)3}4](BF4)3 3.Several 3,5-dimethyltris(pyrazolyl)methane iron(II, III) tricyanide building units have been prepared and characterized. Treatment of K[(HC(3,5-Me2Pz)3)FeII(CN)2](K+ 1- ) with FeII(H2O)6(BF4)2 affords a new anion template cubic cyanometallate cage [(BF4) ⊂ {FeII(H2O)}4{(HC(3,5-Me2Pz)3)FeII (CN)3}4](BF4)3 3.
Keywords: Iron complex; Cyanide; 3,5-dimethyltris(pyrazolyl)methane; Crystal structure;

[HTeV9O28]4 : A new vanadotellurate with decavanadate structure by Saki Konaka; Yoshiki Ozawa; Atsushi Yagasaki (1267-1269).
The first vanadotellurate, [HTeV9O28 ]4− , has been synthesized and structurally characterized. The 51V and 1H NMR revealed that the proton stays on the surface of the molecular oxide anion even in solution.The first vanadotellurate, [HTeV9O28]4 , has been synthesized and structurally characterized. The 51V and 1H NMR revealed that the proton stays on the surface of the molecular oxide anion even in solution.Display Omitted
Keywords: Molecular oxide; Polyvanadate; Tellurate; Proton exchange;

Lithium-mediated ring opening of 1,4-dioxane and structural characterization of a Li12O12 truncated octahedron by John Randazzo; J. Jacob Morris; Jeffrey A. Rood; Bruce C. Noll; Kenneth W. Henderson (1270-1272).
An unusual dodecameric lithium aggregate has been identified as one possible product following the cleavage of 1,4-dioxane by alkyllithium bases.The equimolar reaction of t BuLi with 4-Cl-2,6-Me2-C6H2OH (ArOH) in 1,4-dioxane led to the unexpected formation of the mixed-anion, 1D polymer [(ArO)2(RO)4Li6  · (diox)], 1 (where RO = H2C=C(H)OCH2CH2O). Incorporation of the alkoxy vinyl ether is due to cleavage of 1,4-dioxane by t BuLi. Compound 1 can also be prepared rationally by the reaction of n BuLi with ethylene glycol vinyl ether and ArOH in 1,4-dioxane solution. Direct lithiation of ethylene glycol vinyl ether results in the formation of the alkoxide [ROLi]12, 2. The crystal structure of 2 reveals an unusual truncated octahedral arrangement in the solid state, where each metal is chelated by a vinyl ether subunit.
Keywords: Ether cleavage; Crystal structure; Lithium; Cage compounds; Truncated octahedron;

Two novel coordination polymers {[Zn(bdc)(btb)](H2O)5} n (1) and {[Cd2(bdc)2(btb)(H2O)2](H2O)7} n (2) were synthesized. Coordination polymer 1, a supramolecular isomer of [Zn2(bdc)2(btb)2](H2O)2 [X.L. Wang, C. Qin, E.B. Wang, Z.M. Su, Chem. Eur. J. 12 (2006) 2680], is a special 2D (6,3) network, with six Zn(II) atoms at six corners and four bdc and two double btb at six edges. Coordination polymer 2 exhibits a distorted 3D cubic topology that is built from dimer Cd2 units. The blue luminescent emission maxima at 420 and 439 nm for 1, 440 and 455 nm for 2 were observed in the solid state at room temperature.The self-assembly reactions of the flexible ligand 1,4-bis(1,2,4-triazol-1-yl)butane (btb) and rigid ligand 1,4-benzenedicarboxylate (bdc) with Zn(II) or Cd(II) give two novel coordination polymers {[Zn(bdc)(btb)](H2O)5} n (1) and {[Cd2(bdc)2(btb)(H2O)2](H2O)7} n (2). Coordination polymer 1, a supramolecular isomer of [Zn2(bdc)2(btb)2](H2O)2 [X.L. Wang, C. Qin, E.B. Wang, Z.M. Su, Chem. Eur. J. 12 (2006) 2680], is a special 2D (6,3) network, with six Zn(II) atoms at six corners and four bdc and two double btb at six edges. Coordination polymer 2 exhibits a distorted 3D cubic topology that is built from dimer Cd2 units. The blue luminescent emission maxima at 420 and 439 nm for 1, 440 and 455 nm for 2 were observed in the solid state at room temperature.
Keywords: Supramolecular isomer; Coordination polymer; Zinc complex; Cadmium complex; Bis(1,2,4-triazol-1-yl)butane; Benzenedicarboxylate; Luminescence;

The 1D chain coordination polymer {[Cu(SO4)(dpmd)2] · 8H2O} (1, dpmd = 4,4′-dipyridylmethanediol) has been prepared and characterized. The dpmd ligand was formed in situ from 4,4′-dipyridylketone. Unprecedented decorated C14-type 1D “infinite” water molecule chains were stabilized within the coordination polymer matrix.The 1D chain coordination polymer {[Cu(SO4)(dpmd)2] · 8H2O} (1, dpmd = 4,4′-dipyridylmethanediol) has been prepared by a solution phase method and characterized by single-crystal X-ray diffraction, IR and thermogravimetric analysis. The dpmd ligand was formed in situ from 4,4′-dipyridylketone. Decorated 1D water molecule chains with a very rare C14 classification co-crystallized and were stabilized within the coordination polymer matrix.
Keywords: Coordination polymer; Copper; Crystal structure; Organodiimine; Water chains; Hydrogen bonding;

Anion-dependent assemblies of two unprecedented copper(II) polymers with four-fold screw axes and trapped sodium chains Three Cu(II) coordination polymers [Cu(taa)2] n (1), [Cu(taa)2  · (H2O)4  · Na0.5  · (ClO4)0.5] n (2) and [Cu(taa)2  · (H2O)4  · Na0.5  · (BF4)0.5] n (3) have been synthesized by the reaction of 1H-1,2,4-triazol-1-acetic acid (Htaa) and a series of Cu(II) salts. polymer 1 consists of crossed zigzag chains. In both of polymers 2 and 3, there exist rare four-fold 1-D helical chains, which are induced by ClO 4 - or BF 4 - anions.Three Cu(II) coordination polymers [Cu(taa)2] n (1), [Cu(taa)2  · (H2O)4  · Na0.5  · (ClO4)0.5] n (2) and [Cu(taa)2  · (H2O)4  · Na0.5  · (BF4)0.5] n (3) have been synthesized by the reaction of 1H-1,2,4-triazol-1-acetic acid (Htaa) with different Cu(II) salts. Polymer 1 features a 2-D grid-like network structure constructed by crossed zigzag chains. In both of polymers 2 and 3, there exist rare four-fold 1-D helical chains, which are induced by ClO 4 - or BF 4 - anions. Besides, trapped sodium chains are found to be nested in the channels formed by the intertwist of the helical chains of 2 and 3.
Keywords: Helix; Four-fold axis; Sodium chains; Crystal structure;

The optical properties and the natural lifetime calculation of a Sm(III) complex by Zhefeng Li; Jiangbo Yu; Liang Zhou; Hongjie Zhang; Ruiping Deng (1284-1287).
The emission spectrum from 400 to 1600 nm range of Sm(PM)3(TP)2 in solid (λ ex  = 355 nm) was measured, and the nature lifetime of Sm3+ ion in this complex was determined.The photophysical properties of the complex Sm(PM)3(TP)2 [PM = 1-phenyl-3-methyl-4-isobutyryl-5-pyrazolone, TP = triphenyl phosphine oxide] are determined in crystal state, and energy transfer process is modeled for ligands to center Sm(III) ion. The characteristic luminescence of Sm(III) is sensitized by PM and TP, and most of transitions from excited state 4G5/2 of Sm3+ are detected. According to the Judd–Ofelt theory, values of three oscillator strength parameters were obtained. The radiative transition rates for the emission from 4G5/2 to the lower manifolds were obtained, and calculated radiative lifetime of the 4G5/2 manifold is 3.1 ms. The corresponding fluorescence quantum efficiency is 2.7%.
Keywords: Sm(III) complex; Optical properties; Nature lifetime; Quantum efficiency;

A novel di-copperII-complex substituted monovacant Keggin polyoxotungstate has been hydrothermally synthesized, representing the first magnetic di-transition-metal-complex substituted monovacant Keggin polyoxometalate with a unique 1D dual-bridging chain structure.A novel di-copperII-complex substituted monovacant Keggin polyoxotungstate [Cu(2,2′-bpy)(H2O)][H2PW11O39Cu2(2,2′-bpy)2(H2O)(OH)] · 1.5H2O (1) (2,2′-bpy = 2,2′-bipyridine) with a 1D polymeric chain has been hydrothermally synthesized and structurally characterized. To our knowledge, 1 is the rare magnetic di-transition metal-complex substituted monovacant Keggin polyoxotungstate with a unique 1D dual-bridging chain structure. Its magnetic behavior has been quantitatively analyzed by the Bleaney–Bowers equation, indicating the presence of weak antiferromagnetic interactions within dinuclear CuII centers.
Keywords: Polyoxometalate; Hydrothermal synthesis; Magnetism; Keggin structure;

Synthesis, crystal structure and luminescent properties of new tris-β-diketonate Eu(III) complex with thiadiazolophenanthroline derivative ligand by Hugo Gallardo; Gilmar Conte; Patricia Tuzimoto; Adailton Bortoluzzi; Rosely A. Peralta; Ademir Neves (1292-1296).
The europium (III) complex, [Eu(TTA)3TDPHEN] 1.5CH3CN, where TTA = 2-thenoyl-trifluoroacetone and TDPHEN = [1,2,5]Thiadiazolo[3,4-f][1, 10]phenanthroline, was synthesized and their structure established by single-crystal X-ray diffraction. This complex emit characteristic red light strongly both in solution and in the solid state.Herein we describe the synthesis, characterization and spectroscopic properties of the complex tris-(thenoyltrifluoroacetonate)([1, 2, 5]thiadiazolo[3, 4-f][1,10]phenanthroline) europium(III) acetonitrile solvate, [Eu(TTA)3 TDPHEN] 1.5CH3CN, where TTA = 2-thenoyl trifluoroacetone and TDPHEN = [1, 2, 5]thiadiazolo[3, 4-f][1, 10] phenanthroline. X-ray crystallography reveals that it is an eight-coordinate Eu(III) complex containing three β-diketonate chelates and one N,N′-bidentate ligand, [1, 2, 5] thiadiazolo[3, 4-f][1, 10] phenanthroline. The excitation at 340 nm of the europium complex in a solution of acetonitrile, and at room-temperature, showed the typical Eu(III) red emission as a sharp band at 611 nm, characteristic of Eu(III) due to the transition 5D0  →  7F2. This complex also showed red emission in the solid state phase (λ em  = 612 nm).
Keywords: Luminescence; Europium complex; Thiadiazolo-phenantroline; X-ray crystal structure; β-Diketonates;

Synthesis, structure and norbornene polymerization activity of a bulky β-diketiminato palladium(II) complex by Jeremy A. Olson; Tressia A.P. Paulose; Pia Wennek; J.Wilson Quail; Stephen R. Foley (1297-1299).
A new bulky (β-diketiminato)palladium(II) complex was synthesized by direct reaction of (iPr2Ph)2nacnacH ((iPr2Ph)2nacnac = CH{C(Me)N(C6H3-2,6-iPr2)}2) with Pd(OAc)2. Preliminary investigations into the polymerization of norbornene in the presence of BF3OEt2 were performed.A new bulky β-diketiminato palladium(II) complex was synthesized by direct reaction of (iPr2Ph)2nacnacH ((iPr2Ph)2nacnac = CH{C(Me)N(C6H3-2,6-iPr2)}2) with Pd(OAc)2 which yielded [(iPr2Ph)2nacnac]Pd(OAc) as a mononuclear species with chelating nacnac and acetato ligands. Preliminary investigations into the polymerization of norbornene in the presence of BF3OEt2 were performed.
Keywords: β-Diketiminato; Palladium complex; Nacnac; Polymerization; Norbornene;

Organometallic boxes built from 5,10,15,20-tetra(4-pyridyl)porphyrin panels and hydroxyquinonato-bridged diruthenium clips by Nicolas P.E. Barry; Padavattan Govindaswamy; Julien Furrer; Georg Süss-Fink; Bruno Therrien (1300-1303).
Self-assembly of 5,10,15,20-tetra(4-pyridyl)porphyrin tetradentate panels with dinuclear arene ruthenium clips [Ru26-arene)2(dhbq)Cl2] (arene = C6H5Me, p-PriC6H4Me, C6Me6; dhbq = 2,5-dihydroxy-1,4-benzoquinonato) affords the cationic organometallic boxes of the general formula [Ru86-arene)8(tpp-H2)2(dhbq)4]8+. These cationic cages are isolated as their triflate salts and characterised by mass spectrometry, NMR and IR spectroscopy. The molecular structure was deduced by one and two-dimensional NMR experiments.Self-assembly of 5,10,15,20-tetra(4-pyridyl)porphyrin (tpp-H2) tetradentate panels with dinuclear arene ruthenium clips [Ru26-arene)2(dhbq)Cl2] (arene = C6H5Me, p-PriC6H4Me, C6Me6; dhbq = 2,5-dihydroxy-1,4-benzoquinonato) affords the cationic organometallic boxes [Ru86-C6H5Me)8(tpp-H2)2(dhbq)4]8+ ([1]8+), [Ru86-p-PriC6H4Me)8(tpp-H2)2(dhbq)4]8+ ([2]8+) and [Ru86-C6Me6)8(tpp-H2)2(dhbq)4]8+ ([3]8+). These octanuclear cations have been isolated as their triflate salts and characterised by mass spectrometry, NMR and IR spectroscopy. The molecular structure of these systems was deduced by one-dimensional and two-dimensional NMR experiments (ROESY, COSY, HSQC).
Keywords: Bridging ligands; Arene ligands; Ruthenium; Supramolecular chemistry; Cage compounds;

Refluxing of porphyrin free base with ytterbium (III) acetate hydrate in 1,2,6-trichlorobenzene gives complex A with two solvent molecules coordinating directly to central metal ion. The efficient substitution of solvents by bidentate ligand in A leads to the formation of eight-coordinate complexes B with intense emission in 980 nm.Ytterbium (III) acetylacetonate reacts with 5,10,15,20-tetraphenylporphyrin (H2TPP) and 5,10,15,20-tetra(4-bromophenyl)porphyrin (H2TBrPP) in 1,2,4-trichlorobenzene and forms unexpected acetate-bridged dimer and propionate-coordinated monomer of monoporphyrinate ytterbium (III) complexes, respectively, whereas interaction of ytterbium (III) acetate with H2TPP gives stable acetate-coordinated monomer with two labile methanol binding directly to metal center. This compound reacts readily with 1,10-phenanthroline derivatives to give eight-coordinate monoporphyrinate ytterbium (III) complexes with strong near infrared emission efficiency.
Keywords: Porphyrin; Lanthanide; Near-infrared; Emission; Synthesis;

Solvothermal reaction of N,N′-bis[(pyridin-3-yl)methyl]pyridine-2,5-dicarboxamide (L1 ) as well as Zn(OAc)2 or Co(NO3)2 in methanol gave rise to two new 2D complexes [Zn(L2 )2] n (1) and [Co(L2 )2] n (2), in which in situ formation of an anionic ligand 5-((pyridin-3-yl)methylcarbamoyl)pyridine-2-carboxylate (L2 ) was observed. Single-crystal structural analysis reveals that 1 and 2 are isostructural, and the 2D helical networks are assembled from two different-handed strands with shared common metal atoms. Fluorescent and thermal properties of complexes 1 and 2 are also investigated.Solvothermal reaction of N,N′-Bis[(pyridin-3-yl)methyl]pyridine-2,5-dicarboxamide (L1 ) as well as Zn(OAc)2 or Co(NO3)2 in methanol gave rise to two new 2D complexes [Zn(L2 )2] n (1) and [Co(L2 )2] n (2), in which in situ formation of an anionic ligand 5-((pyridin-3-yl)methylcarbamoyl)pyridine-2-carboxylate (L2 ) was observed. Single-crystal structural analysis reveals that 1 and 2 are isostructural, and the 2D helical networks are assembled from two different-handed strands with shared the common metal atoms. Fluorescent and thermal properties of complexes 1 and 2 are also investigated.
Keywords: Bis(amidopyridine); In situ solvothermal hydrolysis; 2D helical network;