Inorganic Chemistry Communications (v.13, #1)

Contents List (iii-xvii).

A novel three-dimensional vanadium–cobalt phosphate, [C4H12N2]2[CoII(H2O)2(VVO2)2(VIVO)2(PO4)4]·2H2O, was synthesized hydrothermally and characterized by single crystal X-ray diffraction, thermal gravimetric analysis and fluorescence spectroscopes. The three-dimensional vanadium–cobalt phosphate constructed from VIVO6 octahedral chains and VV–CoII–VV clusters which are linked via PO4 tetrahedra. It contains channels in multi-directions in which diprotonated piperazine ions and water molecules reside.A novel three-dimensional vanadium–cobalt phosphate, [C4H12N2]2[CoII(H2O)2(VVO2)2(VIVO)2(PO4)4]·2H2 (1), was synthesized hydrothermally and characterized by single crystal X-ray diffraction, thermal gravimetric analysis and fluorescence spectroscopy. This complex crystallizes in the triclinic system with the space group P 1 ¯ , and cell parameters a  = 7.06610(10) Å, b  = 9.6778(10) Å, c  = 11.6217(2) Å, α  = 106.3260(10)°, β  = 97.8430(10)°, γ  = 107.7070(10)°, Z  = 1. The three-dimensional vanadium–cobalt phosphate is constructed from VIVO6 octahedral chains and VV–CoII–VV clusters which are linked via PO4 tetrahedra, which make complex 1 contain channels in multi-directions in which diprotonated piperazine ions and water molecules reside.
Keywords: Vanadium–cobalt phosphate; Hydrothermal synthesis; Channel; Piperazine;

View of the intermolecular interactions N–H⋯O and O–H⋯O forming polymeric dihydrogendecavanadate(V)–decavanadate(V) chains running along the [ 1 1 ¯ 1 ] axis in [NH2(CH2)4]5[V10O28H2]0.5[V10O28]0.5.A new polymeric compound, [NH2(CH2)4]5[V10O28H2]0.5[V10O28]0.5, was obtained by in situ synthesis of the organic cation from an aqueous solution of V2O5–HCl–NH2(CH2)4NH2. The crystal structure was solved by single-crystal X-ray diffraction. [NH2(CH2)4]5[V10O28H2]0.5[V10O28]0.5 consists of dihydrogendecavanadate(V), [H2V10O28]4−, and decavanadate(V), [V10O28]6−, units assembled in one-dimensional arrays by interanionic hydrogen bonds O–H⋯O and cation-anion N–H⋯O interactions. The latter involve pyrrolidinium cations, which were obtained in the compound instead of the starting butane-1,4-diamine. Pyrrolidinium cations further connect the polymeric chains into a three-dimensional network. The presence of the two types of units, [H n V10O28](6− n )− with n  = 0 and n  = 2, in one compound was not yet observed and is herein reported for the first time.
Keywords: Dihydrogendecavanadate; Decavanadate; Mixed polymeric dihydrogendecavanadate–decavanadate chain; Crystal structure; Transformation of butanediamine to pyrrolidine; Pyrrolidinium;

Influence of symmetric benzene–polycarboxylate acids on the structures of silver-aminopyrimidyl derivative system by Geng-Geng Luo; Di Sun; Na Zhang; Qin-Juan Xu; Li-Rong Lin; Rong-Bin Huang; Lan-Sun Zheng (10-14).
Two novel coordination polymers topologically exhibiting a hexagonal honeycomb 63-hcb and square grid 44-sql net, respectively, have been synthesized by the solution phase reaction of AgNO3 with a mixture of heterocyclic 2-amino-4,6-dimethylpyrimidine (ADMP) and 1,3,5-benzenetricarboxylic acid (H3BTC) or 1,4-benzenedicarboxylic acid (H2BDC) under the ammoniacal conditions and structurally characterized.Two novel coordination polymers, [Ag(BTC)1/3(ADMP)] n (1), [Ag(BDC)1/2(ADMP)] n (2) (2-amino-4,6-dimethylpyrimidine = ADMP; H3BTC = 1,3,5-benzenetricarboxylic acid; H2BDC = 1,4-benzenedicarboxylic acid), have been synthesized under the ammoniacal conditions and structurally characterized. In complex 1, H3BTC ligand showing a new coordination mode links silver atoms to generate a two-dimensional (2-D) honeycomb-like structure, which is further linked through ADMP ligands to produce a complicated three-dimensional (3-D) framework. Complex 2 features a 2-D infinite layer framework consisting of binuclear silver clusters, which is further stacked via intermolecular Cmethyl–H⋯π short contacts and Van der Waals interactions to form a 3-D supramolecular architecture.
Keywords: Silver(I); 2-Amino-4,6-dimethylpyrimidine; 1,3,5-Benzenetricarboxylic acid; 1,4-Benzenedicarboxylic acid; Metal–organic coordination polymer; Photoluminescence;

Under hydrothermal conditions using cis-butenedioic acid (H2L) and corresponding lead(II) salts, a three-dimensional (3D) lead(II) complex {[Pb2(L)(μ2-Cl)(μ3-Cl)]} n (1) containing 3D Pb–X–Pb (X = O and Cl) linkage has been isolated. 1 also represents a truly 3D hybrid luminescent lead(II) framework with I 3 O 0 type connectivity. Further analysis reveals that cis- and trans-conformations of butenedioic acid ligand greatly affect the lead(II) framework structure. Solid-state fluorescence spectrum of 1 exhibits the maximum emission peak at 379 nm.Under hydrothermal conditions using cis-butenedioic acid (H2L) and corresponding lead(II) salts, a three-dimensional (3D) lead(II) complex {[Pb2(L)(μ2-Cl)(μ3-Cl)]} n (1) containing 3D Pb–X–Pb (X = O and Cl) linkage has been isolated. 1 also represents a truly 3D hybrid luminescent lead(II) framework with I 3 O 0 type connectivity. Further analysis reveals that cis- and trans-conformations of butenedioic acid ligand greatly affect the lead(II) framework structure. Solid-state fluorescence spectrum of 1 exhibits the maximum emission peak at 379 nm.
Keywords: cis-Butenedioic acid; 3D Pb–X–Pb linkage; Ligand conformations; Fluorescence;

Two novel Cd(II)-3-BPMFA coordination polymers have been prepared by variations of the solvent molecules. The solvated complex [Cd(μ-3-BPMFA)2Br2] n ·nMeOH (1) exhibits 1D chain containing 32-member macrocycle units. The unsolvated complex [Cd(3-BPMFA)(μ-Br)2]n (2) also features 1D chain, however, the ligand located two sides of Cd–Br chain in different chirality.The bidentate ferrocenyl sandwich molecule N,N′-bis-3-pyridylmethyl-1,1′-ferrocenedicarboxamide (3-BPMFA) has been employed as an organometallic coordination ligand in reaction with CdBr2 to construct heterobimetallic architectures. By assembling the flexible arm-like molecule with CdBr2, two novel bimetallic 1D chain structures are constructed in different solvent systems: the solvated [Cd(μ-3-BPMFA)2Br2] n ·nMeOH (1) from methanol and the unsolvated [Cd(3-BPMFA)(μ-Br)2] n (2) from DMF–Et2O. Different roles of bromine ions have been observed in these two complexes. In 1, bromine ions only act as terminal coordinated ligand, while they play bridging roles in 2. Electrochemistry properties of the ligand and complexes were discussed preliminarily.
Keywords: Ferrocene; Coordination polymer; Cd complex; Electrochemical properties;

Four novel lanthanide(III) coordination polymers with 3D network structures containing 2-fold interpenetration by Wen-Juan Chu; Xiao-Wei Hou; Qing-Huan Zhao; Yao-Ting Fan; Hong-Wei Hou (22-25).
Four novel lanthanide(III) coordination polymers [Ln(L)1.5(H2O)2]·5H2O [Ln = Sm (1), Eu (2), Tb (3), Dy (4)] have been hydrothermally synthesized by the reaction of 1,2-bis[4-amino-5-carboxylmethylthio-(1,2,4-triazol-3-yl)]ethane (H2L) with lanthanide(III) salts. These polymers exhibit 3D network structures with 2-fold interpenetration, in which intriguing 1D channels are observed.Four novel lanthanide(III) coordination polymers [Ln(L)1.5(H2O)2]·5H2O [Ln = Sm (1), Eu (2), Tb (3), Dy (4)] have been hydrothermally synthesized by the reaction of 1,2-bis[4-amino-5-carboxylmethylthio-(1,2,4-triazol-3-yl)]ethane (H2L) with lanthanide(III) salts, and structurally characterized by single crystal X-ray diffraction. Polymers 14 are isostructural, in which all the LnIII atoms are nine-coordinated and the carboxylate groups adopt three different coordination modes (bidentate chelate, bidentate bridging, bidentate chelate bridging) to connect LnIII atoms. These polymers exhibit 3D network structures with 2-fold interpenetration, in which intriguing 1D channels are observed. Besides, the spectra properties of the title polymers are investigated, the strong luminescence characteristics of 23 are found.
Keywords: Coordination polymer; Lanthanide; Crystal structure; Luminescence property;

Tetrameric rhenium complexes with a glycine-thiourea derivative by Jennifer Schroer; Ulrich Abram (26-29).
[ReNCl2(PPhMe2)3] reacts with the glycine ethylester derivative Et2NC(S)NC(Ph)NHCH2COOEt, HL(GlyEt) in methanol under hydrolysis of the ester and formation of syn and anti isomers of the tetrameric, nitrido-bridged rhenium(V) compound [{ReN{fac-L(Gly)}(PMe2Ph)}{ReN{mer-L(Gly)}(H2O)}]2.[ReNCl2(PPhMe2)3] reacts with the glycine ethylester derivative Et2NC(S)NC(Ph)NHCH2COOEt, HL(GlyEt), in methanol under hydrolysis of the ester and formation of the tetrameric, nitrido-bridged rhenium(V) compound [{ReN{fac-L(Gly)}(PMe2Ph)}{ReN{mer-L(Gly)}(H2O)}]2. Both facial and meridional coordination has been found for the tridentate {L(Gly)}2− ligand in the building blocks of the tetramer. Syn and anti isomers with respect to the PPhMe2 ligands have been isolated and characterized by X-ray diffraction.
Keywords: Rhenium; Nitrido complex; Nitrido bridge; Glycine; Thiourea; X-ray structure;

Diverse reactions of S–S function under metal-mediated and metal-free thermolysis conditions by Hai-Bin Zhu; Lei Li; Hai Wang; Xin Lu; Shao-Hua Gou (30-32).
Parallel comparative studies show diverse reactions of S–S function in 2-ppds (2-ppds  = bis(4-(pyridin-2-yl)pyrimidin-2-yl)disulfane) under both metal-mediated and metal-free thermolysis conditions.Parallel comparative studies on reactivities of S–S function in 2-ppds (2-ppds  = bis(4-(pyridin-2-yl)pyrimidin-2-yl)disulfane) have been carried out under the same thermolysis conditions. In the presence of FeCl2, thermolysis reaction of 2-ppds in the MeOH/CH2Cl2 mixture results in a mononuclear compound [FeCl2(2-pps)] with newly generated organic ligand 2-pps (2-pps  = bis(4-(pyridin-2-yl)pyrimidin-2-yl)sulfane). In the absence of FeCl2, the result of solvolysis depends upon the conditions. Thus, in pure MeOH, 2-ppds partially converts into a mixture of S-(4-pyridin-2-yl)pyrimidin-2-yl (4-pyridin-2-yl)pyrimidine-2-sulfonothioate (2-ppst) and 2-pps, while in a MeOH/CH2Cl2 mixture, 2-(chloromethylthio)-4-(pyridin-2-yl)pyrimidine (2-ppct) is the main product.
Keywords: Thermolysis; Disulfide; Reactivity; Bond cleavage; Metal-mediated;

The 2D layer of complex 1 along the bc plane. The layers are extended by C–H⋯O hydrogen bonds to form a 3D framework.Two novel complexes, namely [Cd(L)2] (1) and [Zn(L)2(H2O)2] (2) have been synthesized (HL = 2-(4-isopropyl-4-methyl-5-oxo-4,5-dihydro-1H-imidazol-2-yl)nicotinic acid), which are characterized by elemental analysis, infrared spectrum and X-ray crystal diffraction. While strong hydrogen bonds play central roles in the formation of the 3D structure, the combined influence of the weak interactions such as C–H⋯O bonds, carbonyl⋯π and C–H⋯π interactions are also evident in the structures. The preliminary investigation on the thermal and fluorescence property of the complexes are presented.
Keywords: Fluorescence; C–H⋯π; Carbonyl⋯π; Crystal structure;

A 2D helical coordination polymer based on Keggin-type polyoxoanion: Synthesis, crystal structure and luminescent properties by Dong-Bin Dang; Hui Gao; Yan Bai; Xue-Fu Hu; Fang Yang; Yang Chen; Jing-Yang Niu (37-41).
A new polyoxometalate-based two-dimension helical coordination polymer [Ag(CH3CN)4][Ag3(CH3CN)8(SiMo12O40)] displaying strong fluorescent emission was presented. The form of metal–metal bonds between silver atoms from adjacent helical chains connected the helical chains together into a chiral 2D helical network.A novel two-dimensional helical coordination polymer [Ag(CH3CN)4][Ag3(CH3CN)8(SiMo12O40)] (1) has been gained by the conventional self-assembly reaction, and characterized by IR, elemental analysis, UV, TG technique and X-ray single crystal diffraction. Each [SiMo12O40]4− cluster interconnects with three bimetallic cation subunits through three Mo–O–Ag bridges, meanwhile, each bimetallic cation subunit is surrounded by three [SiMo12O40]4− to form an unprecedented two-dimensional network structure. The metal–metal bonds between Ag(1) and Ag(2) atoms from the adjacent helical chains connects the chains together into a chiral 2D helical network. The 2D network structures are further interconnected with each other to form a 3D supramolecular network through multiform intermolecular hydrogen bonds. The luminescent properties of the coordination polymer in the solid state were investigated.
Keywords: Polyoxometalate; Helical; Coordination polymer; Crystal structure;

A new 2D coordination polymer [Co43-OH)2(H2nip-2H)2(H2nip-H)2(bpe)2] n (1, H2nip = 5-nitro-isophthalic acid, bpe =  trans-1,2-bis(4-pyridyl)ethylene) contained uncommon, rhombic Co(II) tetramer of double T d and double O h geometries, connected by the mixed rigid ligands H2nip and bpe double bridges. The magnetic measurements show that 1 exhibits antiferromagnetic interaction in the tetramer.A new 2D coordination polymer with the formula [Co43-OH)2(H2nip-2H)2(H2nip-H)2(bpe)2] n (1) (H2nip = 5-nitro-isophthalic acid, bpe =  trans-1,2-bis(4-pyridyl)ethylene), has been hydrothermally synthesized and structurally characterized. The structure of 1 is built around uncommon, rhombic {Co4} clusters with double T d and double O h Co(II) geometries, which are extended into 2D network by the rigid deprotonated H2nip and bpe bridges. Magnetic property study indicates there is weak antiferromagnetic coupling interaction between Co(II) ions, which mainly arises from the antiferromagnetic coupling interaction in the tetramer, based on the nature of the μ3-hydroxyl group and synsyn carboxylate-bridged modes.
Keywords: Rhombic Co(II) tetramer; Rigid ligands; Mixed-geometry; Antiferromagnetic;

The highly reduced polyoxoanion [ PMo 5 VI Mo 7 V O 40 Sb 2 III ] 4 - represents the first example of bi-antimony capped α-Keggin phosphomolybdate, which further act as the structure unit for the construction of the interesting 2D inorganic layer through Sb–O secondary bondings. The Sb caps exhibit fundamentally novel Ψ-rhombic pyramidal {SbO4E} hemidirected coordination geometry with coordination number 4.A novel modified POM [ H 4 PMo 7 V Mo 5 VI O 40 Sb 2 III ] (im)2·2H2O (im = imidazole) (1) has been hydrothermally synthesized from the system Sb2O3–H3PMo12O40–H2C2O4–im and characterized by elemental analysis, IR, UV–Vis, XPS, TGA and single crystal X-ray diffraction. The highly reduced polyoxoanion [ PMo 7 V Mo 5 VI O 40 Sb 2 III ] 4 - represents the first example of bi-antimony capped α-Keggin phosphomolybdate, in which the Sb atoms exhibit novel Ψ-rhombic pyramidal {SbO4E} hemidirected coordination geometry with coordination number 4.
Keywords: Bi-antimony capped Keggin structure; Highly reduced polyoxometalate; Hemidirected coordination; Crystal structure;

An organic–inorganic hybrid nickel-substituted arsenotungstate consisting of three types of polyoxotungstate units by Lijuan Chen; Junwei Zhao; Pengtao Ma; Qiuxia Han; Jingping Wang; Jingyang Niu (50-53).
A new organic–inorganic hybrid nickel-substituted arsenotungstate [Na(H2O)3]2[Ni(H2O)6]2[Ni(H2O)5]{[Ni3(dap)(H2O)2]2(H2W4O16)}{(α-H2AsW6O26)[Ni6(OH)2(H2O)(dap)2](B-α-HAsW9O34)}2·7H2O has been hydrothermally synthesized and structurally characterized, which is the interesting polyoxometalate simultaneously containing the trivacant Keggin [B-α-AsW9O34]9−, hexavacant Keggin [α-AsW6O26]11− and tetrameric [W4O16]8− units.A new organic–inorganic hybrid nickel-substituted arsenotungstate [Na(H2O)3]2[Ni(H2O)6]2[Ni(H2O)5]{[Ni3(dap)(H2O)2]2(H2W4O16)}{(α-H2AsW6O26)[Ni6(OH)2(H2O)(dap)2](B-α-HAsW9O34)}2·7H2O (1) (dap = 1,2-diaminopropane) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Crystal data for 1: C18H144As4N12Na2Ni21O176W34, Mr = 11174.92, triclinic, space group P-1, a  = 15.004(4) Å, b  = 16.357(5) Å, c  = 22.070(6) Å, α  = 80.458(5)°, β  = 79.291(5)°, γ  = 72.074(5)°, V  = 5030(3) Å3, Z  = 1, GOOF  = 1.007, R 1  = 0.0703, wR 2  = 0.1670. The skeleton of 1 is a centric nanoscale cluster and is composed of two asymmetric sandwich-type clusters {(α-H2AsW6O26)[Ni6(OH)2(H2O)(dap)2](B-α-AsW9O34)}7− linked by a symmetric cluster {[Ni3(dap)(H2O)2]2(H2W4O16)}6+. Notably, 1 is an interesting polyoxometalate containing the trivacant Keggin [B-α-AsW9O34]9−, hexavacant Keggin [α-AsW6O26]11− and tetrameric [W4O16]8− units. Magnetic measurements indicate that 1 shows the ferromagnetic interactions within NiII centers.
Keywords: Polyoxometalate; Arsenotungstate; Asymmetric sandwich-type cluster; Lacunary Keggin polyoxoanion;

Synthesis, characterization, and applications of novel di-2-pyridyl imine ligands by Jake Yorke; Catlin Dent; Andreas Decken; Aibing Xia (54-57).
Two novel di-2-pyridyl imines, 2,4,6-trimethyl-(di-2-pyridylmethylene)aniline (1) and 2,6-di-isopropyl-(di-2-pyridylmethylene)aniline (2), were prepared through condensation reactions between 2,2′-dipyridyl ketone and 2,4,6-trimethylaniline and 2,6-di-isopropylaniline. They reacted readily with bis(benzonitrile)dichloropalladium(II) to afford palladium imine complexes. The crystal structure of the palladium complex (3) bearing the 2,4,6-trimethyl-(di-2-pyridylmethylene)aniline ligand revealed coordination of a pyridyl group and an imine group to the metal center. The novel ligands were successfully employed in the Suzuki coupling reaction of p-bromoanisole and phenylboronic acid.Two novel di-2-pyridyl imines, 2,4,6-trimethyl-(di-2-pyridylmethylene)aniline (1) and 2,6-di-isopropyl-(di-2-pyridylmethylene)aniline (2), were prepared through condensation reactions between 2,2′-dipyridyl ketone and 2,4,6-trimethylaniline and 2,6-di-isopropylaniline. They reacted readily with bis(benzonitrile)dichloropalladium(II) to afford palladium imine complexes. The crystal structure of the palladium complex (3) bearing the 2,4,6-trimethyl-(di-2-pyridylmethylene)aniline ligand revealed coordination of a pyridyl group and an imine group to the metal center. The novel ligands were successfully employed in the Suzuki coupling reaction of p-bromoanisole and phenylboronic acid.
Keywords: Di-2-pyridyl imines; Phosphine ligands; Palladium complexes; The Suzuki reaction;

Biocompatible Prussian blue nanoparticles: Preparation, stability, cytotoxicity, and potential use as an MRI contrast agent by Mohammadreza Shokouhimehr; Eric S. Soehnlen; Anatoly Khitrin; Soumitra Basu; Songping D. Huang (58-61).
A simple synthetic procedure for preparing biocompatible superparamagnetic Prussian blue (PB) nanoparticles is reported. The stability, cytotoxicity and ability for PB nanoparticles to penetrate cells are investigated. The potential of using PB nanoparticles as the T 1-weighted MRI contrast agent is demonstrated.A simple synthetic procedure for preparing biocompatible superparamagnetic Prussian blue (PB) nanoparticles is reported. The stability, cytotoxicity and ability for PB nanoparticles to penetrate cells are investigated. The potential of using PB nanoparticles as the T 1-weighted MRI contrast agent is demonstrated.
Keywords: Prussian blue; Nanoparticles; Magnetic properties; Contrast agents; Magnetic resonance imaging;

Two new silver(I) complexes, namely [Ag2(μ-dppm)2(μ-SO4)(2-amp)2]·CH3OH (1) and [Ag4(μ-dppm)2(μ-SO4)2(μ-4,4′-bpy)2]·2CH3OH (2) (dppm = bis(diphenyphosphino)menthane, 2-amp = 2-aminopyrimidine, 4,4′-bipy = 4,4′-bipyridine), have been synthesized and characterized. Complex 1 is a 1D polymer, while complex 2 is a tetranuclear cluster.Two new silver(I) complexes containing dppm, nitrogen heterocyclic ligands and sulfate anions, namely [Ag2(μ-dppm)2(μ-SO4)(2-amp)2]·CH3OH (1) and [Ag4(μ-dppm)2(μ-SO4)2(μ-4,4′-bpy)2]·2CH3OH (2) (dppm = bis(diphenylphosphino)methane, 2-amp = 2-aminopyrimidine, 4,4′-bipy = 4,4′-bipyridine), have been synthesized and characterized by IR, X-ray crystallography, luminescence, 1H, 31P NMR spectroscopy. In complex 1, [Ag2(μ-dppm)(μ-SO4)(2-amp)2] binuclear units are linked through robust hydrogen-bond synthon R 2 2 ( 8 ) to give rise to a 1D polymer. While in complex 2, two [Ag2(μ-dppm)(μ-SO4)] units are linked together to form a tetranuclear cluster by two 4,4′-bipyridine ligands.
Keywords: Silver(I); Sulfate; Bis(diphenylphosphino)methane; Nitrogen heterocyclic ligands;

A new sandwich-type polyoxometalate constructed from penta-lacunary [HPW7O28]8− units and MnIII ion by Qiong Wu; Yang-Guang Li; Yong-Hui Wang; Zhi-Ming Zhang; En-Bo Wang (66-69).
The first heptatungstophosphate-based sandwich-type polyoxometalate K12Na[(HPW7O28)2Mn]·17.5H2O has been synthesized, exhibiting good electrocatalytic properties to reduce the nitrite.A new sandwich-type polyoxometalate (POM) K12Na1[(HPW7O28)2Mn]·17.5H2O (1) has been synthesized and characterized by elemental analysis, IR, TG, UV as well as single-crystal X-ray diffraction analysis. Compound 1 represents the first sandwich-type POM constructed by the penta-lacunary heptatungstophosphate [HPW7O28]8− moieties. Moreover, compound 1 exhibits good electrocatalytic properties to reduce the nitrite.
Keywords: Polyoxometalate; Heptatungstophosphate; Sandwich-type; Manganese; Electrocatalysis;

Aldehyde-decorated 2,2′-bipyridine and 2,2′:6′,2″-terpyridine ruthenium(II) complexes: Convenient scaffolds for supramolecular chemistry by Edwin C. Constable; Ana Hernandez Redondo; Catherine E. Housecroft; Markus Neuburger (70-73).
The syntheses, solution spectroscopic properties and single crystal structures of two new aldehyde-decorated tpy and bpy-containing ruthenium(II) complexes, [Ru(1)(bpy)2][PF6]2 and [Ru(1)(tpy)Cl][PF6] (1  = 5,5′-bis(4-formylphenyl)-2,2′-bipyridine) are described.Two new aldehyde-decorated tpy and bpy-containing ruthenium(II) complexes, [Ru(1)(bpy)2][PF6]2 and [Ru(1)(tpy)Cl][PF6] in which 1 is 5,5′-bis(4-formylphenyl)-2,2′-bipyridine, have been prepared and fully characterized. The packing in both solid state structures involves extensive Oaldehyde···HCpyridine contacts, but π-stacking interactions are important only between [Ru(1)(tpy)Cl]+ cations.
Keywords: 2,2′-Bipyridine; 2,2′:6′,2″-Terpyridine; Aldehyde; Ruthenium; Structure;

A strategy for controlling charge and conformation in 2,2′-bipyridine complexes for use in photonic applications by Edwin C. Constable; Catherine E. Housecroft; Markus Neuburger; Jason Price; Adrian Wolf; Jennifer A. Zampese (74-76).
Reaction between H2 1 (H2 1  = 3,3′-dihydroxy-6,6′-dimethyl-2,2′-bipyridine) and [Cu(MeCN)4][PF6] in the presence of [ n Bu4N]Br gives [ n Bu4N][Cu(H1)2]·H2O; in the solid state, the anion comprises a discrete dinuclear {[Cu(H1)2](H2O)2[Cu(H1)2]}2– unit in which two oxygen atoms of each ligand and two water oxygens form a chair shaped, hydrogen-bonded six-membered ring.The complex [ n Bu4N][Cu(H1)2]·H2O (H2 1  = 3,3′-dihydroxy-6,6′-dimethyl-2,2′-bipyridine) is readily formed from the reaction of H2 1 with [Cu(MeCN)4][PF6] in the presence of [ n Bu4N]Br; in the solid state the anion comprises a discrete dinuclear {[Cu(H1)2](H2O)2[Cu(H1)2]}2– unit in which two oxygen atoms of each [H1] ligand and two water oxygens form a chair shaped hydrogen-bonded six-membered ring.
Keywords: Heterocycle; Hydrogen bonding; Copper; Structure; 2,2′-Bipyridine;

Two isomeric cadmium(II) diphosphonates, with the same formula of [Cd(H3L)2] (H4L = (CH3)2N–CH(PO3H2)2), have been synthesized and structurally characterized. One isomer shows a 1D chain structure whereas the other exhibits a novel non-centrosymmetric 3D framework which is formed by a pillared-layer array.Two isomeric cadmium(II) diphosphonates built up from corner-sharing CdO6 octahedra and CPO3 tetrahedra, with the same formula of [Cd(H3L)2] (H4L = (CH3)2N–CH(PO3H2)2), have been synthesized and structurally characterized. Compound 1 shows a 1D chain structure in which the adjacent Cd2+ ions are doubly bridged by two equivalent H3L anions, whereas compound 2 exhibits a novel non-centrosymmetric 3D framework which is formed by a pillared-layer array, with one type of H3L anions participating in the construction of a 21 -symmetry layer and the other type of H3L anions acting as pillars.
Keywords: Cadmium; Diphosphonate; Hydrothermal synthesis; Crystal structure; Isomer;

A series of new Pd(II) complexes bearing 5-methyl-3-(R-1-ylmethyl)-salicylaldimine (R = morpholine, piperidine, pyrrolidine, 4-methylpiperazine, diisopropylamine) have been synthesized and structurally analyzed. These palladium complexes exhibited good catalytic activity in the Suzuki–Miyaura and Heck–Mizoroki coupling reactions in DMF under air.A series of amino-salicylaldimine–palladium(II) complexes bearing 5-methyl-3-(R-1-ylmethyl)-salicylaldimine ligands (R = morpholine, piperidine, pyrrolidine, 4-methylpiperazin, diisopropylamine) have been prepared and characterized by IR, 1H NMR and elemental analysis. Crystal structure details of complex 2b have been confirmed by X-ray structure analysis. The obtained Pd(II) complexes were found to be effective catalysts for the Suzuki and Heck cross-coupling reactions which could be carried out in the undried solvent under air.
Keywords: Suzuki–Miyaura; Heck–Mizoroki; Amino-salicylaldimine; Palladium; Catalysis;

Upon controlling coordination sites of a bipyridinium analogue with different dosage of acid, two Cu(II) complexes with different bridging modes were obtained. Complex 1 is a chain-like coordination polymer with mononuclear centers, while 2 is a dichloro-bridged dinuclear complex, which forms a one-dimensional supramolecular chain via hydrogen bonding. An antiferromagnetic coupling interaction exists in 2.Upon controlling coordination sites of a new bipyridinium analogue 4′-(N-carboxybenzyl-4-pyridinio)-2,2′:6′,2″-terpyridine chloride (HL·Cl) with different dosage of perchloric acid, two copper complexes with distinct bridging modes, {[Cu(L)Cl]·ClO4·3H2O} n (1) and [Cu2(HL)2Cl2]·4ClO4·H2O (2) have been obtained under hydrothermal condition. Complex 1 features a one-dimensional chain-like structure with mononuclear Cu(II) centers, while 2 is a dichloro-bridged dinuclear Cu(II) complex, which forms one-dimensional supramolecular chain via hydrogen bonding interactions between the carboxylic groups of HL ligands. The magnetic measurement reveals that an antiferromagnetic coupling interaction exists in complex 2.
Keywords: Antiferromagnetism; Bipyridinium analogue; Copper; Crystal structure;

Three novel three-dimensional coordination polymers [Cu2(btc)(4,4′-bpt)]·2H2O (1), [Cu(btc)0.5(3,4′-bpt)]·0.5H2O (2) and [Cu(btc)0.5(3,3′-bpt)]·2H2O (3), based on 1,2,4,5-benzenetetracarboxylate acid and three positional isomeric bridging ligands, are prepared and topologically analyzed.Based on 1,2,4,5-benzenetetracarboxylate acid (H4btc), and mixed with three isomeric dipyridyl ligands, three novel 3D Cu(II) coordination polymers [Cu2(btc)(4,4′-bpt)]·2H2O (1) [4,4′-bpt = 1H-3,5-bis(4-pyridyl)-1,2,4-triazole], [Cu(btc)0.5(3,4′-bpt)]·0.5H2O (2) [3,4′-bpt = 1H-3-(3-pyridyl)-5-(4-pyridyl)-1,2,4- triazole] and [Cu(btc)0.5(3,3′-bpt)]·2H2O (3) [3,3′-bpt = 1H-3,5-bis(3-pyridyl)-1,2,4-triazole] have been synthesized and characterized, respectively. 1 is a 3D pillared double-layer complex containing a novel bilayer unit; 2 is a 3D pillared-layer architecture with (4,4)-sql layer; 3 exhibits a 3D structure containing 3D [Cu(btc)] motif and 1D [Cu(bpt)] chain. The topological analysis shows that 1 can be simplified to a (4,6)-connected network with the Schläfli symbol of (42·64)2(48·67), 2 a (4,6)-connected network with the symbol of (44·62)(44·610·8), and 3 a four-connected topology with the symbol of (32·103·11)2(32·104).
Keywords: Cu(II) complex; Positional isomer; Crystal structure; Topological analysis;

A porous lanthanide metal–organic framework with luminescent property, nitrogen gas adsorption and high thermal stability by Gang Wang; Tianyou Song; Yong Fan; Jianing Xu; Miao Wang; Liping Wang; Lirong Zhang; Li Wang (95-97).
[Eu2(BDC)3(DMF)2]·(DMF)1.7 has one-dimensional hexagonal channels and high thermal stability. Moreover, it emits red light in solid state at room temperature and has good adsorption property of nitrogen gas.A novel lanthanide metal–organic framework, [Eu2(BDC)3(DMF)2]·(DMF)1.7(BDC = 1,3-benzenediacarboxylate) 1 has been synthesized under solvothermal condition and characterized by single-crystal X-ray structure determination, luminescent property, nitrogen gas adsorption, powder X-ray diffraction, IR, and TGA.
Keywords: Rare-earth; Porous materials; Metal–organic frameworks; Nitrogen gas adsorption; Luminescent property;

A new multi-cobalt-substituted C-shaped polyoxotungstogermanate, [((CoOH2)Co2GeW9O34)2(GeW6O26)]20− by Tong Ruizhan; Lili Chen; Ying Liu; Bin Liu; Ganglin Xue; Huaiming Hu; Feng Fu; Jiwu Wang (98-100).
Polyanion [((CoOH2)Co2GeW9O34)2(GeW6O26)]20− consists of two [B-α-(CoOH2)Co2GeW9O34]4− units linked via a unique B-type hexavacant GeW6O26 12− fragment, leading to a C-shaped structure with C 2 v symmetry. This is the first report of the C-shaped multi-cobalt-substituted polyoxotungstogermanate.A new multi-cobalt-substituted polyoxogermanotungstate Na20[((CoOH2)Co2GeW9O34)2(GeW6O26)]·47H2O has been synthesized and characterized by IR spectroscopy, UV electronic and luminescent spectroscopy, elemental analysis and single-crystal X-ray diffraction. Polyanion [((CoOH2)Co2GeW9O34)2(GeW6O26)]20− consists of two [B-α-(CoOH2)Co2GeW9O34]4− units linked via a unique B-type hexavacant GeW6O26 12− fragment, leading to a C-shaped structure with C 2 v symmetry. This is the first report of the C-shaped multi-cobalt-substituted polyoxotungstogermanate.
Keywords: Polyoxometalates; Structure elucidation; Cobalt; Germanium; Sandwich-type;

Novel chains constructed from heterotrinuclear units and 1,2-bis(4-pyridyl)ethane formulated as [M2M′(O2CPh)6](bpa) (M = Co, Zn, M′ = Co, Cd): Their catalytic activity by Young Min Lee; Young Joo Song; Jung In Poong; Soo Hyun Kim; Hyo Geun Koo; Jung Ah Lee; Cheal Kim; Sung-Jin Kim; Youngmee Kim (101-104).
Three novel heterometallic complexes formulated as [M2M’(O2CC6H5] n (bpa) n (M2M′ = Zn2Co (1), Zn2Cd (2), and Co2Cd (3)) have been synthesized. All three compounds show one-dimensional structures containing linear heteronuclear coordination units linked by bridging bpa ligands. Reactivity study of the compounds 13 for the transesterification of a variety of esters has shown that they are very efficient and 2 is the best among them.Three novel heterometallic complexes containing two bridging ligands bpa and benzoate, formulated as [M2M′(O2CC6H5] n (bpa) n (bpa = 1,2-bis(4-pyridyl)ethane, M2M′ = Zn2Co (1), Zn2Cd (2), and Co2Cd (3)), have been synthesized. All three compounds show one-dimensional structures containing linear heteronuclear coordination units linked by bridging bpa ligands. Reactivity study of the compounds 13 for the transesterification of a variety of esters has shown that they are very efficient and 2 is the best among them.
Keywords: Heterometallic complex; One-dimensional chain; 1,2-Bis(4-pyridyl)ethane; Transesterification;

Two isomeric Au complexes of S-trithiane: One-dimensional polymer assembled through aurophilic interactions by Cheng-Yang Yue; Wan-Dong Chen; Fei-Long Jiang; Rui Feng; Mao-Chun Hong (105-108).
Two isomeric Au complexes, [Au(Stt)Cl] n (1) and [Au(Stt)Cl]4 n (2) (Stt = S-trithiane), have been prepared and structurally and spectroscopically characterized. Complexes 1 and 2 feature 1D nearly linear chains and flexural chains composed of Au(Stt)Cl molecules via varying aurophilic interactions, respectively. Luminescent spectrums illuminate both red emissions of the title complexes at room temperature.Two isomeric Au complexes, [Au(Stt)Cl] n (1) and [Au(Stt)Cl]4 n (2) (Stt = S-trithiane), have been prepared and structurally and spectroscopically characterized. Each compound crystallizes as a unique form with aurophilic interactions between the linear and two-coordinated Au(I) cations. In complex 1, the Au(Stt)Cl molecules self-associate to form 1D nearly linear chains via equivalent aurophilic interactions, whereas the structure of complex 2 features 1D flexural chains composed of zigzag [Au(Stt)Cl]4 tetramers through varying aurophilic interactions. Emission spectra of both complexes at room temperature give strong red luminescence.
Keywords: Supermolecule; Polymer; Gold(I); S-trithiane; Aurophilicity; Luminescence;

Synthesis, structure and magnetic property of a cyanamido bridged trinuclear copper complex by Ling-Chen Kang; Xin Chen; Xiao-Yu Chen; You Song; Jing-Lin Zuo; Xiao-Zeng You (109-111).
An unusual μ 1,1,3-cyanamido bridged trinuclear copper(II) complex, [(2,2′-bipyridine)6Cu3(NCN)](ClO4)4·H2O, has been prepared and structurally characterized. Magnetic studies show the existence of strong antiferromagnetic coupling.An unusual μ 1,1,3-cyanamido bridged trinuclear copper complex, [(2,2′-bpy)6Cu3(NCN)](ClO4)4·H2O (1) (2,2′-bpy = 2,2′-bipyridine), has been synthesized and structurally characterized. Magnetic studies show the existence of large antiferromagnetic coupling between the copper(II) ions.
Keywords: Crystal structures; Copper(II) complexes; Cyanamido ligand; Magnetic properties; Polynuclear complexes;

Two novel metal-organic frameworks [Cd2(hdb)2(1,4-ndc)2] n (1) and [Ni3(Hhdb)2(1,4-ndc)4(H2O)2] n (2) (hdb = 1,1′-(1,6-hexanediyl)bis(imidazole) and 1,4-ndc = 1,4-naphthalenedicarboxylate) show 2D parallel interpenetration and 3D CsCl-type topology, respectively, which are mainly affected by the differences of the metal centers.Two novel metal-organic frameworks [Cd2(hdb)2(1,4-ndc)2] n (1) and [Ni3(Hhdb)2(1,4-ndc)4(H2O)2] n (2) have been synthesized under the similar hydrothermal conditions (hdb = 1,1′-(1,6-hexanediyl)bis(imidazole) and 1,4-ndc = 1,4-naphthalenedicarboxylate). The polymers (1) and (2) show 2D parallel interpenetration and 3D CsCl-type topology, respectively, which are mainly affected by the differences of the metal centers.
Keywords: Coordination polymer; 1,1′-(1,6-Hexanediyl)bis(imidazole); Parallel interpenetration; CsCl-type topology;

The first example of extended structure constructed from Knoth-type sandwich POMs and coordination fragments by Guo-Wu Wang; Cheng-Ling Pan; Ke-Chang Li; Xiao-Bing Cui; Hai-Tao Wang; Yan Wang; Shu-Yun Shi; Ji-Qing Xu (116-118).
A novel compound containing the first example of extended structure constructed from Knoth-type sandwich polyoxoanions and transition metal coordination complexes has been hydrothermally synthesized.A novel compound [P2W18M3O68][Cu(en)2]4·7H2O·2OH (M = 0.5W + 0.5Cu) 1 which contains the first example of extended structure constructed from Knoth-type sandwich polyoxoanions and transition metal coordination complexes has been hydrothermally synthesized and characterized by elemental analysis, IR spectrum, UV–Vis spectrum and single-crystal X-ray diffraction analysis. Crystal data for 1: triclinic, space group, P-1, a  = 13.2718(7) Å, b  = 13.6432(8) Å, c  = 25.7307(15) Å, α  = 104.7340(10)°, β  = 96.7630(10)°, γ  = 90.0330(10)°, V  = 4472.2(4) Å3, Z  = 2. Structure solution and refinement based on 1090 parameters gave R1 (wR2) = 0.0409 (0.0993).
Keywords: Polyoxometalate; Hydrothermal synthesis; Sandwich polyoxoanions; Knoth-type; POMs in extended structure;

The reaction of the metal carbonyls Fe2(CO)9 or Ru3(CO)12 with 1-isocyano-1-methyl-cyclohexane produces the octahedral metal(II) cyano complexes [M(CN)2(1-CH3-C6H10-NC)4] in good yields. The cis-isomer is not isolated as a pure compound due to rearrangement processes that yield the sterically less crowded trans-isomer.The reaction of the metal carbonyls Fe2(CO)9 or Ru3(CO)12 with 1-isocyano-1-methyl-cyclohexane produces the octahedral metal(II) cyano complexes [M(CN)2(1-CH3-C6H10-NC)4] in good yields. The cis-isomer is not isolated as a pure compound due to rearrangement processes that yield the sterically less crowded trans-isomer. The molecular structure of the trans-isomer of the ruthenium complex shows the expected almost ideal octahedral coordination of the central ruthenium ion with two cyanide and four isocyanide ligands. This reaction again indicates that isocyanides exhibiting quarternary carbon atoms in α-position with respect to the isocyano substituent in general react with di- or trinuclear metal carbonyls to yield cyano complexes with oxidized metal centres and concomitant reductive cleavage of the respective isocyanide.
Keywords: Iron; Ruthenium; Cyanide; Isocyanide; X-ray;

Bis(3,5-dimethylpyrazol-1-ylpropan-1-one forms palladium dichloride complex, which readily undergoes C–H activation to from an N^C^N pincer palladium complex, and thus demonstrates the potential of this pyrazolyl compound as a tridentate ligand.Four new bis(3,5-dimethylpyrazol-1-yl)alkanones were prepared by the reaction of the respective alkanoyl chloride with 3,5-dimethylpyrazole: L1 from chloropropionyl chloride, L2 from 4-chlorobutyryl chloride, L3 from oxalyl chloride and L4 from adipoyl dichloride; all in moderate yields. Of the four compounds only L1 successfully reacts with [PdCl2(NCMe)2] to yield [PdCl2(L1)] in 41% yield, which on heating in toluene leads to C–H activation to produce [PdCl(L1′)], where L1′ is deprotonated L1, in very low yield.
Keywords: Bis(3,5-dimethylpyrazolyl)alkanone; Palladium(II) chloride complexes; C–H activation; Crystal structures;

A novel heteronuclear complex {[K[Cd(dci)2(H2O)2]6]Cl} n (1), has been successfully synthesized and characterized. There are two kinds of coordination modes of dci ligands in 1: bidentate bridging and tridentate bridging. It is through the bridging function of dci ligands that K(I) and Cd(II) ions are connected and 3D coordination polymer of 1 forms. Its fluorescent emission properties are also studied here.A novel heteronuclear cooordination polymer containing potassium and cadmium, {[K[Cd(dci)2(H2O)2]6]Cl} n (1) (Hdci = 4,5-dicyanoimidazole), has been synthesized and characterized with the aid of elemental analysis, fluorescence spectroscopic studies and single-crystal X-ray diffraction. In compound 1, half of dci anions act as bidentate bridging ligands and the other half act as tridentate bridging ligands. It is through the bridging function of dci ligands that K(I) and Cd(II) ions are connected and 3D coordination polymer of 1 forms. Solid-state fluorescence measurements reveal that complex 1 can emits strong purple emission band.
Keywords: 4,5-Dicyanoimidazole; Potassium; Cadmium; Coordination polymer; Fluorescence;

Kinetics of Ag(I) catalyzed oxidation of amino acids by peroxomonosulphate by S. Maria Rayappan; D. Easwaramurthy; M. Palanichamy; V. Murugesan (131-133).
The order of reaction was found to be unity with respect to [PMS] and fractional for both [AA] and [Ag+]. The rate equation was derived and thermodynamic parameters were calculated and discussed.Silver(I) catalyzed oxidation of amino acids such as glycine and α-alanine by peroxomonosulphate (PMS) in aqueous perchloric acid medium was found to be first order in [peroxomonosulphate] and fractional order in [amino acid] and [Ag(I)]. The rate equation was derived by assuming equilibrium formation of adduct between amino acids and Ag(I). This adduct was presumed to react with PMS in a slow step to yield (adduct)2+, which was self-oxidized in a fast step to give the products. The kinetic results revealed that silver catalyzed reaction occurred approximately 104 times faster than the uncatalyzed reaction and this is attributed to the formation of (adduct)2+. The bimolecular rate constant (k) for the slow step and the activation parameters were calculated and the results are discussed.
Keywords: Oxidation; Peroxomonosulphate; Ag(I); Amino acid; HClO4;

Dehydrogenation of 1,3-cyclohexadiene photocatalyzed by osmocene by Horst Kunkely; Arnd Vogler (134-136).
Osmocene acts as a photocatalyst for the dehydrogenation of 1,3-cyclohexadiene which yields benzene and hydrogen. It is suggested that the primary photochemical step is an electron transfer from the excited osmocene to the diene.Osmocene acts as a photocatalyst for the dehydrogenation of 1,3-cyclohexadiene which yields benzene and hydrogen. It is suggested that the primary photochemical step is an electron transfer from the excited osmocene to the diene.
Keywords: Dehydrogenation; Photocatalysis; Osmocene; 1,3-Cyclohexadiene;

Photoreduction of carbonate in a copper(I) complex by Horst Kunkely; Arnd Vogler (137-138).
The photolysis of (prophos)CuI(CO3)CuI(prophos) with prophos = 1,3-bis(diphenylphosphino)-propane in homogeneous solution leads to the reduction of carbonate according to a simple overall stoichiometry (CO2  + prophos → CO + prophos monoxide). It is suggested that this reaction is initiated by a ( Cu I → CO 3 2 - ) MLCT state.The photolysis of (prophos)CuI(CO3)CuI(prophos) with prophos = 1,3-bis(diphenylphosphino)-propane in homogeneous solution leads to the reduction of carbonate according to a simple overall stoichiometry (CO2  + prophos → CO + prophos monoxide). It is suggested that this reaction is initiated by a ( Cu I → CO 3 2 - ) MLCT state.
Keywords: Coordination chemistry; Copper(I); Photochemistry; Carbonate reduction;

A photoluminescent three-dimensional (3D) AgI coordination polymer {[Ag6(L)(μ3-hmt)24-hmt)2(ClO4)](ClO4)4(H2O)} (1), exhibiting an unusual (3,4)-connected (6·7·8)2(4·6·7)2(4·7·8)2(72·8)2(62·7·83)(62·72·8·10) topological network, has been successfully constructed (L  = 2-naphthol-5-carboxylate and hmt = hexamethylenetetramine). Moreover, the luminescent properties of 1 have also been investigated.The reaction of AgClO4 with 2-naphthol-5-carboxylic acid (HL) and hexamethylenetetramine (hmt) in the presence of 2,6-dimethylpyridine afforded a photoluminescent three-dimensional (3D) AgI polymer {[Ag6(L)(μ3-hmt)24-hmt)2(ClO4)](ClO4)4(H2O)} (1), which exhibited an unusual (3,4)-connected (6·7·8)2(4·6·7)2(4·7·8)2(72·8)2(62·7·83)(62·72·8·10) topological network (L  = 2-naphthol-5-carboxylate). Moreover, the luminescent properties of 1 have been briefly investigated.
Keywords: Silver(I) complex; Naphthalene-based ligand; Crystal structure; Topology; Luminescence;

New multinuclear europium(III) complexes as phosphors applied in fabrication of near UV-based light-emitting diodes by Huihui Wang; Pei He; Shenggui Liu; Jianxin Shi; Menglian Gong (145-148).
Two new multinuclear europium(III) complexes was synthesized and characterized. A bright red LED was successfully fabricated by coating the complex onto InGaN chip. All these results suggest that the Eu(III) complexes are promising candidates as red component for application in fabrication of near UV-based white light-emitting diodes.Two new multinuclear europium(III) complexes, [Eu(AFTFBD)3]2(1,4-bmb) and [Eu(AFTFBD)3]3(tmb) were designed and synthesized, where HAFTFBD was 2-acetylfluorene-4,4,4-trifluorobutane-1,3-dione, 1,4-bmb was 1,4-bis[2-(2′-pyridyl)benzimidazolyl]benzene and tmb was 1,3,5-tris[2-(2′-pyridyl)benzimidazolyl]benzene. The complexes were characterized by IR, UV–visible, photoluminescence (PL) spectroscopy and thermogravimetric analysis (TGA). The complexes emit the characteristic red luminescence of Eu3+ ion due to the 5 D 07 FJ (J  = 0–4) transitions under 395 nm-light excitation. Bright red light-emitting diodes were fabricated by coating the selected complex (Eu(AFTFBD)3)3(tmb) onto ∼395 nm-emitting InGaN chips, and the LEDs show appropriate CIE chromaticity coordinates in red area. All these results suggest that the Eu(III) complexes are promising candidates as red component for application in fabrication of near UV-based white light-emitting diodes.
Keywords: Neutral ligand; Eu(III) complex; Phosphor; Luminescence; LED;

A ferrocene-glycine conjugate, 2-[(methoxycarbonyl)methyl]-2-aza[3]ferrocenophane (see the crystal structure), was obtained by Ru-catalysed condensation 1,1′-bis(hydroxymethyl)ferrocene with glycine methyl ester and was structurally characterised by a combination of spectroscopic methods, X-ray crystallography and cyclic voltammetry.A new type of ferrocene–amino acid conjugate, 2-[(methoxycarbonyl)methyl]-2-aza[3]ferrocenophane (1), was obtained in a rather low yield via condensation reaction of 1,1′-bis(hydroxymethyl)ferrocene and glycine methyl ester in the presence of [RuCl2(PPh3)3] as a catalyst. The compound was characterised by combustion analysis and by spectroscopic method, and its solid-state structure was established by single-crystal X-ray diffraction analysis. Compound 1 is reluctant towards alkylation with MeI but readily forms a stable picrate salt. Cyclic voltammetry experiments on 1 (in CH3CN at Pt electrode) revealed the compound to undergo a one-electron reversible oxidation attributable to ferrocene/ferrocenium couple (E o′ = −5 mV vs. ferrocene itself), which shifts towards more positive potentials upon protonation with HCl.
Keywords: Ferrocene; Glycine; Ferrocenophane; Structure elucidation; Cyclic voltammetry;

By reaction of 2-iodo-3-nitrophenol with methylene iodide and Ullmann intramolecular coupling of the produced 1,1′-[methylenebis(oxy)]bis[2-iodo-3-nitro]benzene the compound 1,11-dinitro-dibenzo[d,f] [1,3]dioxepine was obtained and characterized by single crystal X-ray analysis. The diamine produced by reduction of the nitroderivate gave a complex also examined by X-ray diffraction analysis. Resolution of the enantiomers of the diamino ligand can be easily attained by use of tartaric acid.Reaction of 2-iodo-3-nitrophenol with methylene iodide and Ullmann intramolecular coupling of the produced 1,1′-[methylenebis(oxy)]bis[2-iodo-3-nitro]benzene afforded 1,11-dinitro-dibenzo[d,f] [1,3]dioxepine, characterized by single crystal X-ray analysis. The title diamine was obtained by reduction of the nitroderivate with hydrazine hydrate. Resolution of the enantiomers of the novel C2-symmetric ligand can be easily obtained by use of tartaric acid. A test on the coordinating ability of the diamine has produced a complex examined by X-ray diffraction analysis.
Keywords: Atropoisomerism; Dioxepine; Platinum; Resolution;

A tubular luminescent Zn(II) coordination polymer with unsymmetrical bridge ligand by Ben-Lai Wu; Rui-Ying Wang; E. Ye; Hong-Yun Zhang; Hong-Wei Hou (157-159).
A novel 1D tubular coordination polymer [ZnL(dca)2] n constructed by the unsymmetrical bridge ligands L spirally winding around two double-chain pillars Zn(dca)2 was synthesized and characterized.A novel 1D tubular coordination polymer [ZnL(dca)2] n (dca = dicyanamide, L = 2-(3-pyridylmethylthio)-5-(4-pyridyl)-1,3,4-oxadiazole) constructed by the unsymmetrical bridge ligands L spirally winding around two double-chain pillars Zn(dca)2 was synthesized and characterized.
Keywords: 1,3,4-Oxadiazole derivative; Unsymmetrical ligand; 1D tubular coordination polymer; Fluorescence properties;

The first azido-bridged mixed-valent cobalt defective double cubane cluster complex was synthesized and characterized structurally and magnetically.The new azido-bridged cobalt cluster complex, [ Co 2 II Co 2 III μ 1 , 1 - N 3 ) 4 ( N 3 ) 2 ( HDMSP ) 2 ( MeOH ) 2 ] · 2 H 2 O (H3DMSP = 1,3-dihydroxy-2-methyl-2-(salicylideneamino)propane), is the first azido-bridged mixed-valent cobalt complex showing a defective double cubane structure. Magnetic study indicated that there is an antiferromagnetic interaction between two Co2+ ions.
Keywords: Cubane cluster complex; Azido bridge; Mixed valence cobalt complex; Crystal structure; Magnetic property;

A new open-framework zinc arsenate [C4N3H16]2[Zn5(AsO4)4(HAsO4)2] by V. Koteswara Rao; Srinivasan Natarajan (163-166).
A new open-framework zinc arsenate with an interrupted zeolite-like structure is describedA three-dimensional zinc arsenate with an interrupted zeolitic framework (−IIO), [C4N3H16]2[Zn5(AsO4)4(HAsO4)2], I has been synthesized solvothermally. The structure is built up from ZnO4, AsO4 and HAsO4 tetrahedral units connected alternatively through their vertices forming the 3-D structure possessing one-dimensional channels bound by 10 T-atoms (T = Zn, As). The framework density of the structure is 10.4 T-atoms which indicates considerable openness in its structure.
Keywords: Solvothermal synthesis; Crystal structure; Interrupted framework; Characterization;

An unprecedented mixed-type of azametallacrown based on a flexible pentadentate N-propionyl end ligand was reported, which exhibits not only the completely different arrangement of the metal centers but also diverse geometric configurations of the N-terminal ligands, and which was further assembled into novel 3-D supramolecular structure via various intermolecular interactions.A mixed-type of azametallacrown based on a flexible pentadentate N-propionyl ligand was reported, which exhibits not only the completely different arrangement of the metal centers but also diversely geometric configurations of the N-terminal ligands, and this complex can further assemble into a novel 3-D supramolecular structure using two different aza18-MC-6 as secondary building units (SBUs) via the intermolecular C–H⋯π, π–π and C–H⋯O interactions. Temperature-dependent magnetic susceptibility measurements of the title complex indicate that the complex presents significantly antiferromagnetic coupling among metal centers.
Keywords: Metallacrown; Diversely geometric configuration; Mixed-type of azametallacrown; Supramolecular structure;

One-dimensional salen-type heterospin trimetallic (3d–4f–3d′) chain-like coordination polymers: Syntheses, crystal structures and magnetic properties by Wen-Bin Sun; Peng-Fei Yan; Guang-Ming Li; Ju-Wen Zhang; Ting Gao; Masayuki Suda; Yasuaki Einaga (171-174).
A series of novel cyano-bridged one-dimensional salen-type heterospin trimetallic (3d–4f–3d′) chain-like polymers [{LCu(H2O)}Ln(MeOH)(H2O)2{(μ-CN)2Fe(CN)4}]·2H2O (1, Ln = La; 2, Ln = Nd; 3, Ln = Gd) were synthesized and characterized by elemental analysis, IR spectra and X-ray single-crystal diffraction. The magnetic investigation for 3 indicated a ferrimagnetic chain may form.Three one-dimensional (1D) heterospin trimetallic chain-like polymers [{LCu(H2O)}Ln(MeOH)(H2O)2{(μ-CN)2Fe(CN)4}]·2H2O (1, Ln = La; 2, Ln = Nd; 3, Ln = Gd) were prepared by substitution of the nitrato ligands in [LCuLn] complexes with [Fe(CN)6]3− ions (H2L =  N,N′-bis(3-methoxysalicylidene)propane-1,2-diamine). Single-crystal X-ray diffraction analysis revealed that the methyl on the salen-type ligand impeded the connection between cyanide groups and Cu(II) ions efficiently. Consequently, three novel one-dimensional (1D) trimetallic chain-like polymers were obtained with the linker [Fe(CN)6]3− ions interacting only with the lanthanide ions. The magnetic investigation for 3 indicated a ferrimagnetic chain may form.
Keywords: Salen-type ligand; Heterospin; Trimetallic polymer; Structure; Magnetic properties;

Employing the tetrapodal compound 1,2,3,4-tetra(4-pyridyl)thiophene (TPT) as a bridging ligand, a new metal–organic framework was obtained and characterized by single crystal X-ray diffraction, [Cd(TPT)(N3)2·(H2O)] (1). It exhibits a 2D layer network constructed from the three-connector TPT and EE azido bridges. It also displays good thermal stability and strong photoluminescence in the blue regionband thus may serve as a candidate of thermally stable blue-light-emitting electroluminescence material.Employing the tetrapodal compound 1,2,3,4-tetra(4-pyridyl)thiophene (TPT) as a bridging ligand, a new metal–organic framework was obtained and characterized by single crystal X-ray diffraction, [Cd(TPT)(N3)2·(H2O)] (1). This polymer exhibits a 2D layer network and an unprecedented 3,4-connected topology, which is constructed from the three-connector TPT and EE azido bridges. It also displays good thermal stability and strong photoluminescence in the blue regionband thus may serve as a candidate of thermally stable blue-light-emitting electroluminescence material. The nature of electronic transitions in the photoluminescent process has also been investigated by means of time-dependent density functional theory (TDDFT) calculations and molecular orbital analyses, which shows that the luminescent property is ligand-based.
Keywords: Cadmium(II) complex; Crystal structure; Tetradentate ligand; Luminescence; TDDFT;

The photoluminescence spectra of iridium (III) complexes with novel ancillary ligands cover almost the whole visible range with blue, blue–green, and red emissions.A series of iridium (III) complexes incorporating novel ancillary ligands have been synthesized and fully characterized by IR, 1H NMR, HRMS and elemental analysis. The crystal structures of 1 and 4 have been determined by X-ray analysis. The photoluminescence spectra of 14 show emission maxima at 501, 414, 592 and 504 nm, respectively, which cover almost the whole visible range, as a consequence of the nature of the fused imidazo-carboxylate ancillary ligands. In particular, 3 is an effective constituent for the multi-component white light phosphorescent materials, because it can simultaneously emit three colors (blue, blue–green, and red) and cover the whole visible range from 400 to 600 nm.
Keywords: Iridium (III) complexes; Phosphorescence color tuning; Crystal structures; Phosphorescent emitting materials; White light material;

The redox properties of three heteroleptic Pt(II) complexes were investigated: [Fe(C5H4PPh2)2]Pt(BzT)2 where BzT = benzenethiolate (BT), 2,3,5,6-tetrafluorobenzenethiolate (TFBT) and 3,5-dimethylbenzenethiolate (DMBT), correlating with the electron-withdrawing capability of the monothiolate ligands.Three heteroleptic Pt(II) complexes with 1,1′-bis(diphenylphosphino)ferrocene (dppf) and benzene-monothiolate (BzT) ligands such as benzenethiolate (BT), 2,3,5,6-tetrafluorobenzenethiolate (TFBT) and 3,5-dimethylbenzenethiolate (DMBT), (dppf)Pt(BzT)2, were synthesized from (dppf)PtCl2 and the corresponding benzene-monothiols. X-ray structural analysis of (dppf)Pt(TFBT)2 showed that the two TFBT ligands are parallel and in an anti-conformation with respect to a slightly distorted P2PtS2 plane. The redox properties of the three Pt(II) complexes are correlated with the electron-donating capability of the monothiolate ligands. The more-electronegative TFBT ligand induces a short Pt–P bond distance (2.273(2) Å), a large Pt–P coupling constant (J Pt–P  = 3171 Hz) and a high oxidation potential ( E pa 3 = 1.355 V ). A charge-transfer complex of (dppf)Pt(DMBT)2 was prepared by the reaction with F4TCNQ and characterized.
Keywords: Pt(II) complex; Benzenethiolate; Electrochemistry; X-ray crystal structures;

Photoinduced electron transfer in panchromatic zinc phthalocyanine–azobenzene dyad by Yizhu Liu; Hong Lin; Xin Li; Jianbao Li; Hui Nan (187-190).
A new unsymmetrical azobenzene–phthalocyanine dyad was designed and synthesized. Efficient uni-directional transfer of photoelectron from azobenzene π* orbital to phthalocyanine S 1 orbital was unexpectedly recorded.A new unsymmetrical azobenzene–phthalocyanine dyad was designed and synthesized. Besides impressive panchromatic absorptivity both in solution and adsorbed on solid-state anatase TiO2 substrate, efficient photoinduced electron transfer from azobenzene π* orbital to phthalocyanine S 1 orbital was elucidated for the first time by fluorescence spectroscopy and cyclic voltammetry. Such an interesting phenomenon as a dominant intra-molecular electronic communication process is attributed to the inefficiency of local deactivation pathway through orbital overlap forbidden π* →  n transition. This may imply efficient collection of panchromatic photoelectrons by delicate molecular design and is expected to boost fields related to solar energy utilization.
Keywords: Azobenzene; Phthalocyanine; Panchromatic; Photoinduced electron transfer;

A red luminescent organic–inorganic hybrid network with double-stranded zigzag [Cu4I4] n chains by Chun-Feng Yan; Fei-Long Jiang; Lian Chen; Rui Feng; Ning Li; Mao-Chun Hong (191-194).
A novel red luminescent coordination polymer, [Cu2I2(bmt)] n ·nDMF (1), was synthesized. Single-crystal analysis shows that its unusual organic–inorganic hybrid framework is built-up from the distorted double-stranded zigzag [Cu4I4] n chains with organic bmt ligands. Emissive properties of 1 in solid state at room temperature and 10 K were investigated.A novel red luminescent coordination polymer, [Cu2I2(bmt)] n ·nDMF (1), was synthesized from the solution reaction of CuI and heterocyclic thione ligand, benz-1,3-imidazole-2-thione (bmt). Single-crystal analysis shows that its unusual organic–inorganic hybrid framework built-up from the distorted double-stranded zigzag [Cu4I4] n chains with organic bmt ligands. Emission properties of 1 in solid state at room temperature and 10 K were investigated.
Keywords: Cu(I) coordination polymer; Organic–inorganic hybrid; Heterocyclic thione ligand; Luminescence;

Cobalt complexes in [EMIM]Cl – A catalyst for oxidation of alcohols to carbonyls by Dileep Ramakrishna; Badekai Ramachandra Bhat (195-198).
Cobalt (II)-Schiff base complexes with triphenylphosphine were effective in the oxidation of primary and secondary alcohols in ethyl-methyl-imidazolium ionic liquid medium in presence of NaOCl.A coordination complex system consisting of Cobalt (II)-Schiff bases with triphenylphosphine were synthesized and characterized. These catalysts were effective in the oxidation of primary and secondary alcohols. The oxidation reactions were carried out in ethyl-methyl-imidazolium ionic liquid in presence of NaOCl. Higher catalytic activity was observed for CoL1.
Keywords: Co(II) complexes; Schiff base; Catalytic oxidation; Green oxidation;

Two novel complexes, Na3Y(pydc)3·12H2O (1) and Y2(pydc)(OH)4·3H2O (2) (pydc = 2,6-pyridinedicarboxylate), have been synthesized by the reaction of yttrium (III) nitrate with pydcH2 in different molar ratios, and characterized by elemental analysis and IR. Thermal decompositions and antimicrobial activities against Bacillus coli and Staphylococcus aureus have been recorded and interpreted for both. The crystal structure of complex 1 is determined by single crystal X-ray diffraction and the possible structure of complex 2 is also described.Two novel complexes, Na3Y(pydc)3·12H2O (1) and Y2(pydc)(OH)4·3H2O (2) (pydc = 2,6-pyridinedicarboxylate), were synthesized by yttrium (III) nitrate and pydcH2 with different molar ratios. The elemental analysis, IR spectra and single crystal X-ray diffraction were used to determine the structure of complexes. The thermal decompositions and antimicrobial activities against Bacillus coli and Staphylococcus aureus were recorded and interpreted for both.
Keywords: Yttrium (III); 2,6-Pyridinedicarboxylic acid; Coordination complex; Crystal structure; Antibacterial activity;

Copper(II) complexes of Schiff base ligands derived from 2,2′-dimethylpropandiamine have been prepared and characterized. These complexes catalyze the oxidation of cyclooctene and styrene using tert-butylhydroperoxide as oxidant in good yields. Various parameters such as solvent and concentration of oxidant have been optimized. Excellent selectivity of epoxidation for cyclooctene and good selectivity for styrene was obtained.Two square planar copper(II) complexes of tetradentate Schiff base ligands derived from aromatic aldehydes and 2,2′-dimethylpropandiamine (H2{salnptn(3-OMe)2}, H2{hnaphnptn}) have been prepared and used as catalysts for oxidation of cyclooctene and styrene with tert-butylhydroperoxide (TBHP). Oxidation of cyclooctene with TBHP gave cyclooctene oxide as the sole product, but in the case of styrene a mixture of styrene oxide and benzaldehyde has been obtained in ca. 1:3 molar ratio. It has been shown that the rate and selectivity of reaction depend to the electron-donor ability of substituents at the phenyl groups of the ligand and can be improved by introduction of π-electron-donating groups at the aromatic rings of salen-type Schiff bases. The structure of Cu{salnptn(3-OMe)2} has been determined by X-ray crystallography at 291 K with results generally in agreement with those previously reported. The results suggest that the symmetrical Schiff base ligands are bivalent anions with tetradentate N2O2 donors derived from the phenolic oxygen and azomethine nitrogen atoms.
Keywords: Schiff base; Copper(II) complexes; Catalyst; Oxidation; tert-Butylhydroperoxide;

Thin films of a dimeric ruthenium phthalocyanine complex on gold by Tristan Rawling; Christine E. Austin; Hadi M. Zareie; Andrew M. McDonagh (208-210).
A new dimeric ruthenium phthalocyanine complex bearing a thioester-functionalized axial ligand has been synthesised and characterised. We show that the new complex forms thin films on gold surfaces.Thin films of a new dimeric ruthenium phthalocyanine complex bearing a thioester-functionalized axial ligand were formed on gold surfaces. Characterization of the thin films by laser ablation-inductively coupled-mass spectrometry and scanning tunneling microscopy revealed that the films do not have any long-range order.
Keywords: Ruthenium; Phthalocyanine; Thin film; Gold;

Self-assembly of a novel 3D copper(I)-tetrazolate supramolecular framework via interpenetration of porous 2D double-layer motifs by Quan-Guo Zhai; Shu-Ni Li; Xia Gao; Wen-Juan Ji; Yu-Cheng Jiang; Man-Cheng Hu (211-214).
A novel 3D organic–inorganic hybrid supramolecular solid constructed from interpenetrating (3,4,5)-connected 2D porous nets, namely, [Cu6(TAZ)4(CN)2] n (1) (TAZ = tetrazole) was successfully synthesized under hydrothermal conditions and characterized by X-ray single-crystal diffraction, elemental analysis, FT-IR, Raman spectrum, DT/TGA and solid state photoluminescence measurements.The self-assembly of CuCN and 1H-TAZ ligand under hydrothermal conditions generated a novel three-dimensional hybrid supramolecular framework, namely, [Cu6(TAZ)4(CN)2] n (1) (TAZ = tetrazole). Single-crystal X-ray diffraction show that [Cu2(TAZ)2] binuclear subunits are linked by μ2- and μ3-CN groups to give a 2D double-wave-shaped network, which possesses 1D channels with four open-windows. The 2D bilayers interpenetrated each other to form the 3D supramolecular framework of 1.
Keywords: CuCN; Tetrazole; Supramolecular framework; Interpenetration; Luminescence;