Inorganic Chemistry Communications (v.7, #1)

Contents List (iii-vi).

A novel gas inclusion solid was generated by cooling an empty host crystal of copper(II) benzoate–pyrazine in a carbon dioxide environment and characterized by single-crystal X-ray diffraction analysis.
Keywords: Dinuclear Cu complex; Coordination polymer; Inclusion compound; Crystal structure; Carbon dioxide;

The first neutral Sn(II) complex derived from a pentadentate thiosemicarbazone ligand by Manuel R Bermejo; Rosa Pedrido; M Isabel Fernández; Ana M González-Noya; Marcelino Maneiro; M Jesús Rodrı́guez; Marı́a J Romero; Miguel Vázquez (4-8).
The electrochemical oxidation of a tin plate in the presence of an acetonitrile suspension of the ligand bis-(4-N-methylthiosemicarbazone)-2,6-diacetylpyridine, H4DAPTsz-Me, yields the complex Sn(H2DAPTsz-Me)(H2O)2 (1). Recrystallisation of 1 in a methanol/acetone solution leads us to isolate yellow crystals of [Sn(H2DAPTsz-Me)(CH3OH)2] · CH3OH (2), structurally characterised. To the best of our knowledge, 2 is the first neutral Sn(II) complex derived from a pentadentate thiosemicarbazone Schiff base ligand. This complex shows a distorted pentagonal bipyramidal geometry for Sn(II), being the metal surrounded by the N3S2 donor set of the bideprotonated ligand [H2DAPTsz-Me]2−. This compound self-assembles into a 3D network through intermolecular hydrogen bonds.
Keywords: Thiosemicarbazone; Schiff base ligands; Tin; Pentagonal bipyramidal geometry; 3D network;

Dicarboxylato-bridged diruthenium units in two different oxidation states: the first step towards the synthesis of Creutz–Taube analogs with dinuclear Ru2 n+ species by Panagiotis Angaridis; John F Berry; F.Albert Cotton; Peng Lei; Chun Lin; Carlos A Murillo; Dino Villagrán (9-13).
Two compounds having two Ru2(DAniF)3 units (DAniF=N,N -di-p-anisylformamidinate) linked by terephthalate anions have been made. Reaction of (NBu4)2O2CC6H4CO2 with the mixed-valence, mixed-ligand species Ru2(DAniF)3(O2CCH3)Cl (1) gives a compound with the formula [Ru2(DAniF)3Cl]2(O2CC6H4CO2) (2) in which the two diruthenium units are formally Ru2 5+, while in the second compound the diruthenium units have been reduced with zinc powder so that the formula is [Ru2(DAniF)3Cl0.12]2(O2CC6H4CO2) (3). The magnetic properties of 1 and 2 have been studied and the crystal structures of 2 and 3 are reported. All three compounds are electrochemically active.
Keywords: Metal–metal bonds; Diruthenium complexes; Magnetism; Crystal structure; Electronic communication;

Reaction of the asymmetrical pyridine–imine ligand L (where L=benzoic acid, 3-[(2-pyridinylmethylene)amino]) with W(CO)3(EtCN)3 and CO (g) affords a W(0) tetracarbonyl in which the Schiff-base ligand coordinates in a bidentate fashion. The complex was characterized by IR, NMR, and UV–visible spectroscopy and elemental analysis. The solid-state structure of W(CO)4(L), which crystallized in the orthorhombic space group Pbca with unit cell parameters a=22.497(4) Å, b=14.112(6) Å, and c=13.675(3) Å was established by X-ray crystallography. Deprotonation of the –CO2H group on the ligand with base results in the formation of a water-soluble organometallic complex which can be partitioned between organic and aqueous phases in a biphasic system by pH adjustment.
Keywords: Pyridinylimine ligand; Tungsten(0) complex; Water-soluble complex; Phase transfer;

Interaction of divalent metal acetylacetonates, M(acac)2, M=Mg, Co, with titanium methoxide, Ti(OMe)4, in 1:1 ratio in toluene provides with practically quantitative yield a new family of heterometallic alkoxide complexes with general composition M2Ti2(acac)4(OMe)8, M=Mg (1), Co (2). The structure of these nearly spherically shaped molecules contains both metals in octahedral coordination, one acac-ligand being attached to each metal atom. Both 1 and 2 are highly soluble in hydrocarbon solvents and display considerable volatility with distinct fragmentation patterns starting from molecular ions in the mass-spectra, which makes them perspective precursors of titanate materials in sol–gel and MOCVD techniques.
Keywords: Heterometallic alkoxides; Bimetallic alkoxides; Magnesium titanate; Cobalt titanate; Molecular structure;

Synthesis, structure and spectral properties of a novel molybdoantimonate NaSbMoO5 by Yongjing Wang; Hanhui Zhang; Changcang Huang; Qiaozheng Sun; Xiaohong Yu (21-23).
A novel compound NaSbMoO5 has been synthesized by hydrothermal method and structurally characterized by X-ray crystallography. The structure contains layers made up of MoO4 and SbO4 units while sodium cations reside between two layers. IR, UV–Vis DRIS, fluorescent spectra and the thermogravimetric analysis of this compound were investigated.
Keywords: Molybdoantimonate; Hydrothermal synthesis; Crystal structure; Photoluminescence;

Hydrothermal reaction of lanthanum(III) sulfate with oxalic acid at 180 °C resulted in a novel 3D lanthanum(III) sulfate oxalate, La2(C2O4)(SO4)2(H2O)3, in which the lanthanum(III) ions are interconnected via oxalate and sulfate groups to form a novel 3D network of lanthanum(III) sulfate–oxalate hybrid.
Keywords: Structure; Hydrothermal synthesis; Lanthanum; Sulfate; Oxalate;

A first μ-NO3 bridged and self-assembled 2-D silver (I) complex [Ag(I)(im-mPy)NO3)] (1) (im-mPy=(2-(3-pyridyl)-4,4,5,5-tetramethyl-2-imidazolin-1-ol), has been prepared and structurally characterized. Temperature dependence of susceptibility measurements shows a weak ferromagnetic coupling between im-mPy radicals with J=3.3 cm−1.
Keywords: Imino nitroxides; Silver complexes; Crystal structure; Magnetic properties; Self-assembly; H-bonding;

Crystal structure and fluorescence of a novel 3D inorganic–organic hybrid polymer with mixed ligands by Xiu-Jie Liu; Qian-Rong Fang; Guang-Shan Zhu; Mine Xue; Xin Shi; Gang Wu; Ge Tian; Shi-Lun Qiu; Lin Fang (31-34).
A new inorganic–organic hybrid polymer [Cd3(CTC)2(4,4-bipy)2(C2H5OH)2] n (1) (CTC=cis,cis-1,3,5-cyclohexanetricarboxylate and 4,4-bipy=4,4-bipyridine) that exhibits intense fluorescent property was synthesized under appropriate conditions and characterized by single-crystal X-ray diffraction, which revealed a 3D architecture formed by 4,4-bipy ligands interlinked adjacent 2D sheets [Cd3(CTC)2(C2H5OH)2] n .
Keywords: Inorganic–organic hybrid polymer; Crystal structure; Fluorescence; Mixed ligands;

The complex ethylenebis(indenyl)zirconium(IV) binolate with binol=1,1-binaphthyl-2,2-diol is characterized by a lowest-energy ππ binolate IL (intraligand) excited state (absorption λ max=348 nm). The IL triplet undergoes an emission at λ max=490 nm under ambient conditions.
Keywords: Electronic spectra; Luminescence; Charge transfer; Zirconium complexes; Phenolate complexes;

The ambidentate (S,S)- or (P,S)-bidentate ligand, 3-diphenylphosphane-carbothioyl-1,1-dimethyl-thiourea (HL), has been prepared, and the solid state and solution structures of its nickel(II) complex, NiL2, investigated. In the solid state the nickel(II) centre is square-planar and the ligand is coordinated in the (S,S)-bidentate mode, whereas in chloroform solution an equilibrium mixture of three isomers is rapidly formed, in which a (P,S)-bidentate species is the major component.
Keywords: Nickel(II); Ambidentate ligands; Dithiobiuret; Phosphines;

The complex chloroacetatotris(N,N -diphenylformamidinato)diruthenium(II,III), [Ru2Cl(μ-O2CMe)(μ-DPhF)3] (1), has been isolated in the reaction of [Ru2Cl(μ-O2CMe)4] with N,N -diphenylformamidine (HDPhF) in thf. This complex is an intermediate in the total substitution process of acetate ligands in [Ru2Cl(μ-O2CMe)4] by formamidinate groups. The remaining acetate can be substituted by other ligands, allowing the use of compound 1 as starting material for other tris(formamidinato)diruthenium complexes. The syntheses and crystal structures of 1  ·  HDPhF, 1  ·  2thf, and [Ru2Cl(μ-O2CC6H4OC10H21)(μ-DPhF)3] (2) are reported.
Keywords: Diruthenium compounds; Metal–metal bonds; Formamidinato complexes; Ruthenium complexes; Acetate complexes;

Synthesis of a new series of poly-2,2-bipyridinyl ruthenium(II) complexes with polytopic ligands derived from 4-methyl-2,2-bipyridine by Jean-Claude Lepretre; Bamba Bar; Jérôme Chauvin; Alain Deronzier; Bertrand Lefebvre (47-50).
Five novel disymmetrical ligands containing two or more 2,2-bipyridine moieties covalently linked, belonging to 4, 5 or 8 coordination sites, have been synthesized with high yield, starting from previously prepared 4-methyl-2,2-bipyridine. Their abilities to complex ruthenium(II) have been investigated as well as the determination of the main physico-chemical features of the resulting multinuclear complexes.

Two 2D, 3D cadmium-pyridinedicarboxylate polymers: structures and photoluminescent properties by Sheng-Qing Xia; Sheng-Min Hu; Jing-Cao Dai; Xin-Tao Wu; Jian-Jun Zhang; Zhi-Yong Fu; Wen-Xin Du (51-53).
Two Cd(II)-pyridinedicarboxylate polymers have been synthesized by hydrothermal reaction. They present novel structural motifs and exhibit intense fluorescent emissions upon photoexcitation.
Keywords: Coordinate polymers; Cadmium; Ligand;

Synthesis, structure and magnetic properties of a novel ferromagnetic cluster [FeV6O6{(OCH2CH2)2N(CH2CH2OH)}6]Cl2 by M.Ishaque Khan; Saadia Tabussum; Robert J Doedens; Vladimir O Golub; Charles J O’Connor (54-57).
■■■A rarely observed ferromagnetic polyoxocationic cluster, [FeV6O6{(OCH2CH2)2N(CH2CH2OH)}6]Cl2, composed of metallocyclic core and containing an array of six d1 ions {V(IV)} around high spin d6(FeII) center, exhibiting useful magnetic properties has been synthesized and fully characterized.
Keywords: Ferromagnetic clusters; Polyoxovanadates; Anderson structure; Crystal structure;

The compound [Cu(en)2]1.5[H3As6V15O42(H2O)] · 3H2O 1 (en=ethylenediamine) has been synthesized and characterized by elemental analysis, IR spectrum and single crystal X-ray diffraction analysis. Crystal structure analysis reveals that compound 1 is not only the first example of one-dimensional sinusoidal chain structure constructed from polyoxometalates and coordination complex fragments but also the first example of one-dimensional chain of polyoxometalates where clusters are connected by one coordination complex fragment and two coordination complex fragments alternatively.
Keywords: Hydrothermal synthesis; Polyoxometalate; Arsenic–vanadium cluster; One-dimensional chain; Crystal structure;

Preparation of Co2+:MAl2O4/SiO2 (M=Zn, Mg) nanocomposites by sol–gel method by Xiulan Duan; Duorong Yuan; Xiufeng Cheng; Caina Luan; Zhihong Sun; Xuecheng Wei; Shiyi Guo; Dong Xu; Mengkai Lv (62-64).
Co2+:MAl2O4/SiO2 (M=Zn and Mg) nanocomposites, containing nanocrystalline Co2+-doped MAl2O4 dispersed in silica glass matrix, were obtained by sol–gel method, and the corresponding precursor gels were prepared by using two different aluminum salts as starting materials. Co2+:ZnAl2O4 nanocrystals were precipitated when the gels were heated up to 900 °C, and the crystallite size is in the range of 9–20 nm, depending on the heat-treatment temperature and the aluminum salt grades. When using aluminum-iso-propoxide (Al(OPri)3) as starting material, Co2+:MgAl2O4 nanocrystals were formed by heating the gels above 1000 °C. Co2+ ions were located in tetrahedral sites in ZnAl2O4 (or MgAl2O4) nanocrystals replacing Zn2+ (or Mg2+) ions.
Keywords: Sol–gel; Nanocomposite; X-ray diffraction; Absorption spectra;

A dinuclear ruthenium–dioxolene complex which undergoes two reversible ligand-centred redox processes was anchored to the surface of a nanocrystalline Sb-doped SnO2 electrode to make a window which is polyelectrochromic in the visible and near-infrared regions.
Keywords: Dinuclear ruthenium–dioxolene complex; Polyelectrochromic; Nanocrystalline SnO2 electrode;

The first metal complex of 5-hydroxyorotic acid: dimethylammonium bis(N,N-dimethylformamide) bis(5-hydroxyorotato(-2))gallate(III) by Giannis S. Papaefstathiou; Sia Manessi; Catherine P. Raptopoulou; Edward J. Behrman; Theodoros F. Zafiropoulos (69-72).
Reaction of Ga(acac)3 with 5-hydroxyorotic acid dihydrate (5-hydroxy-2,6-dioxo-1,2,3,6-tetrahydropyridimine-4-carboxylic acid dihydrate, LH4  · 2H2O) in DMF yields the mononuclear complex (CH3)2NH2[Ga(LH2)2(DMF)2] · H2O · 0.4DMF (1). X-ray crystallographic analysis showed that the octahedral anion [Ga(LH2)2(DMF)2] self-assembles through hydrogen bonds to form a 2D anionic framework; the cation (CH3)2NH2 + derives from the hydrolysis of the solvent. Complex 1 is the first crystallographically characterized 5-hydroxyorotate complex of any metal, and also the first Ga(III) complex with an orotate-type ligand.
Keywords: Bioinorganic chemistry; Crystal structure; Gallium complexes; 5-hydroxyorotic acid; Metal orotate complexes;

Preparation of nanoparticulate metal catalysts in porous supports using an ionic liquid route; hydrogenation and C–C coupling by Kris Anderson; Silvia Cortiñas Fernández; Christopher Hardacre; Patricia C Marr (73-76).
Aerogels containing palladium metal nanoparticles were prepared using an ionic liquid route and tested for activity towards hydrogenation and Heck C–C coupling reactions.
Keywords: Heck; C–C coupling; Hydrogenation; Nanoparticles; Aerogel; Ionic liquids;

The reaction of pyterpy with an excess of cadmium(II) nitrate yields the novel mononuclear complex [Cd(pyterpy)(H2O)(NO3)2]. The crystal structure shows to the Cd(II) centre in a seven-coordinate environment and the molecular units behaving as supramolecular nodes. These neutral nodes are connected through aromatic π-stacking interactions concerted with O–H⋯N(4-pyridyl) and O–H⋯O(nitrate) hydrogen bonds to give couples of parallel linear strips assembled in a zipper-like motif. The infinite strips are oriented in the same direction and each one interact weakly with their neighbors by means of C–H⋯O hydrogen bonds to form the crystal. The supramolecular product is highly insoluble in the most common organic solvents and water, but soluble in dimethyl sulfoxide where the intermolecular interactions are broken.
Keywords: Cadmium(II) complexes; Polypyridine complexes; π-stacking; Supramolecular chemistry; 4-(4-pyridyl)-2,2:6,2′′-terpyridine;

Structure, spectroscopic, and magnetic properties of copper(II) dinuclear complex with μ-hydroxo and μ-pyrazolato bridges by Magdalena Zarȩba; Krzysztof Drabent; Zbigniew Ciunik; Stanisław Wołowiec (82-85).
The crystal and molecular structure of dinuclear complex [Cu2(DBM)2(μ-pz)(μ-OH)] (where: DBM – dibenzoylmethanate, pz – pyrazolate) was determined by X-ray diffraction method. Structure of [Cu2(DBM)2(μ-pz)(μ-OH)] consists of dinuclear unit in which the copper(II) ions are linked in the plane by N,N -bridging pyrazolato and hydroxo anions. Terminal chelating dibenzoilomethanate anions are κ 2 bound via oxygen atoms to each copper(II). The intradimer Cu(II)–Cu(II) distance and Cu(II)–O(OH)–Cu(II) angle are equal to 3.321(1) Å and 121.2(3)°, respectively. The dimers form stacks with short interdimer Cu(II)–Cu(II) contact of 3.535(1) Å. The variable-temperature magnetic susceptibility measurements (2–300 K) for a powdered sample of the complex were interpreted on the basis of the spin-hamiltonian yielding 2J=−217.8 cm−1, g=2.102, p=0.39%. The interdimer magnetic coupling was included to give antiferromagnetic coupling constant zJ =−91.2 cm−1. The value of −2J observed in [Cu2(DBM)2(μ-pz)(μ-OH)] results from counterbalance between two different bridges in molecule.
Keywords: Copper(II) dimer; Structure; Magnetism; Antiferromagnetic interaction;

Simple, high yield and reagent-saving synthesis of pure α-K6P2W18O62  · 14H2O by Israel-Martyr Mbomekalle; Yu Wei Lu; Bineta Keita; Louis Nadjo (86-90).
A new, simple, high yield and reagent-saving synthesis of α-K6P2W18O62  · 14H2O was achieved by preforming metatungstate from Na2WO4  · 2H2O before adding slowly the appropriate excess of H3PO4 4M. Direct precipitaton with KCl was followed by redissolution of the crude solid in Millipore water and prolonged heating at 80 °C in a pH < 2 medium. The yield is almost quantitative, based upon the original amount of sodium tungstate. Keys to the maximization of the yield are also the PW ratio, the initial [H+–WO4 2−] ratio, the pH of the reaction mixture. To facilitate discussion, an excess parameter R * is defined as the ratio between the actual PW ratio and the stoichiometric value of this parameter in the complex. It is demonstrated that the value of R * can be substantially diminished compared to its values in the previous literature, provided the pH of the reaction mixture is properly controlled.
Keywords: IR; 31P and 183W NMR; Cyclic voltammetry; α-K6P2W18O62  · 14H2O; Wells–Dawson heteropolyanion;

Antimony-doped tin oxide (ATO) nanoparticles were successfully synthesized by the coprecipitation method from the starting materials granulated tin and Sb2O3 for the first time.
Keywords: Tin oxide; Antimony; Doping; Unit cell parameters; Coprecipitation; Synthesis;

A new mixed-ligand coordination polymer, {[Cu(BDC)(Phen)(H2O)] · (H2O)(DMF)} n 1 (BDC = 1,4-benzenedicarboxylate; Phen = 1,10-phenanthroline) has been synthesized and characterized. It was found that the complex 1, crystallized in orthorhombic crystal system, was transformed into a more stable compound due to the evaporation of inclusion solvents in air, {[Cu(BDC)(Phen)(H2O)] 2, and the complex 2 was characterized in triclinic crystal system. Complex 1: space group Pnma with unit cell dimensions a=23.378(2), b=12.830(1) and c=6.984(1) Å, Z=4. Complex 2: space group P 1 ̄ with unit cell dimensions a=9.004(1), b=10.527(1) and c=10.577(1) Å, α=114.779(1), β=92.246(1), γ=114.746(1), Z=2.
Keywords: Coordination polymer; One-dimensional structure; Two-dimensional structure; Structural transformation; Copper coordination polymer; Hydrogen bonds;

Activation of C–H bond by cis-[Pt(NO3)2(PPh3)2], cyclometallation of tetramethylthiourea by Serena Fantasia; Mario Manassero; Alessandro Pasini (97-100).
Reaction of cis-[Pt(NO3)2(PPh3)2] with tetramethylthiourea affords deprotonation of an NCH3 group and cyclometallation via the sulfur atom and the CH2 residue, as evidenced by X-ray crystallography. The role of the dissociation of the labile nitrato groups, to give cationic intermediates, is outlined.Reaction of cis-[Pt(NO3)2(PPh3)2] with tetramethylthiourea (tmtu) affords [Pt(PPh3)2(tmtu*)]NO3, in which tmtu* is tetramethylthiourea deprotonated at one methyl group. An X-ray investigation has shown that tmtu* is cyclometallated with Pt–S and Pt–CH2 bonds. The likely role of dissociation of the labile nitrato ligands, to give cationic intermediates, is outlined.
Keywords: Cyclometallated tetramethylthiourea; Platinum-nitrato-phosphine complex; X-ray structure;

Synthesis and structure of carboxylate-bridged polynuclear copper(II)–lanthanum(III) ring: [La(H2O)5(CuL)2][CuL] · 8H2O by Yang Zou; Wen-long Liu; Chun-Lin Ni; Zhao-Ping Ni; Yuan-Gen Yao; Qing-Jin Meng (101-103).
Reaction of the Na[CuL] (where L= Schiff base derived from 5-bromosalicylaldehyde and glycylglycine) with LaCl3  ·  nH2O leads to the formation of the title complex 1 [La(H2O)5(CuL)2][CuL] · 8H2O which containing ring-like hexa-nuclear [La2(H2O)10(CuL)4]2+ cation.
Keywords: Cu(II)–La(III) complex; Hexa-nuclear cation; Crystal structure; Dipeptide;

Reaction of copper(II) chloride with picolinic acid N-oxide (HL) in acetone/THF mixed solvent afforded a novel layered compound, [Cu(L)Cl(H2O)]2, in which each pair of octahedrally coordinated copper(II) ions are bridged by two N-oxide groups to form a Cu2O2 dimeric unit, and such dimeric units are further interconnected via carboxylate groups to form a layer.
Keywords: Copper complex; Crystal structure; Cu2O2 dimer; Layered compound; Magnetic property;

■■■The diacid/diamide derivative trans-1,2-bis{carboxymethyl-[2-(2,3-dihydro-indol-1-yl)-2-oxoethyl]-amino}-cyclohexane (H2L) of the hexadentate complexone ligand trans-1,2-diaminocyclohexane-tetraacetic acid, and its nickel(II) and iron(III) complexes have been prepared. The nickel(II) complex [NiL] has a distorted octahedral geometry and the iron(III) complex [FeL(H2O)][NO3] has a seventh ligand (water), to give a distorted pentagonal bipyramidal geometry.
Keywords: Iron complexes; Nickel complexes; Complexone ligands; Dexrazoxane;

The reaction of nido-1-Na(TMEDA)-2-(Si(CH3)3-3-(CH3)-2,3-C2B4H5, with anhydrous HgCl2 in a 2:1 carborane to metal molar ratio produced the bridged compound μ,μ-[2-(Si(CH3)3)-3-(CH3)-2,3-C2B4H5]2 Hg (1). The structure of 1 was determined by single crystal X-ray diffraction that showed the compound to have C2 symmetry, with each carborane being η2-bonded to the mercury center.
Keywords: Mercuracarborane; Metallacarborane; d10-Carborane; Bridged-complex; Nido-carborane cage; Crystal structure;

A solvothermal synthesis and structure of K2Ag2GeS4 with the simplest helical chains by Yonglin An; Menghe Baiyin; Xin Liu; Min Ji; Cuiying Jia; Guiling Ning (114-116).
A novel helical chain compound K2Ag2GeS4 was synthesized solvothermally. This compound crystallizes in the monoclinic system, space group C2/c, with a=13.2935(1) Å, b=6.3590(9) Å, c=12.4010(2) Å, β=122.118(10)°, Z=4. It comprises of the simplest helical chains formed by tetrahedral GeS4 and 2-coordinated bridging Ag+ ions.
Keywords: Solvothermal synthesis; Quaternary thiogermanates; Chiral chains;

Modification of electron transfer properties in photoelectrochemical solar cells by substituting {Ru(terpy)2}2+ dyes with thiophene by Egbert Figgemeier; Viviane Aranyos; Edwin C. Constable; Robyn W. Handel; Catherine E. Housecroft; Christian Risinger; Anders Hagfeldt; Emad Mukhtar (117-121).
The addition of 2-thienyl substituents to carboxyphenyl {RuII(terpy)2} dyes in photoelectrochemical solar cells has a profound effect upon the efficiency of photoinduced electron injection into the TiO2 conduction band. This effect can be explained by a change in the character of the LUMO when the 2-thienyl substituent is added to the complex. This is evidenced by electrochemical data and supported by semi-empirical calculations.A comparison of the properties of the 2-thienyl-substituted carboxyphenyl {RuII(terpy)2} dyes with their non-substituted analogues has enabled us to gain insight into the electronic properties that are prerequisite for efficient electron injection into the TiO2 conduction band in photoelectrochemical solar cells. Introducing the thienyl group has a profound effect upon the efficiency of photoinduced electron injection. This effect can be explained by a significant shift in the LUMO position from the terpy ligand anchored on the TiO2 surface towards the 2-thienyl substituted ligand, which is shown by means of electrochemistry and semi-empirical calculations.
Keywords: 2,2:6,2-Terpyridine; 2-Thienyl-2,2:6,2-terpyridine; Electron transfer; Photoelectrochemical solar cells; TiO2 surface;

Increased electron deficiency of MnIIMnIII 2 core by trichloroacetate in [Mn3O(O2CCCl3)6(H2O)3] leads to formation of a reductive coupled MnII 4MnIII 2 mixed-valent hexanuclear cluster [Mn6O2(O2CCCl3)10(H2O)3(HOCH2C6H5)] · 2CH3C6H5 in toluene.
Keywords: Oxo-centered manganese clusters; Reductive coupling; Oxidation of toluene; Magnetic properties;

A crystalline solid, [Rh(II)2(bza)4(1,5-nptd)] n (bza and 1,5-nptd=benzoate and 1,5-naphthyridine), was synthesized and characterized by single-crystal X-ray diffraction analysis; the microporous compound demonstrates gas adsorbency with a N2 BET surface area of 291.6 m2 g−1.
Keywords: Microporous solid; Crystal structure; Gas adsorption; Dinuclear Rh complex; One-dimensional polymer;

A novel one-dimensional vanadium arsenate grafted with the directly coordinated organonitrogen ligands: [(VO)2(HAsO4)2(phen)2] (phen=phenanthroline) by Yu Hou; Yongge Wei; Enhong Shen; Dongrong Xiao; Enbo Wang; Shutao Wang; Yangguang Li; Lin Xu; Changwen Hu (128-130).
A novel organic–inorganic hybrid vanadium arsenate [(VO)2(HAsO4)2(phen)2] 1 (phen=phenanthroline) has been hydrothermally synthesized and structurally characterized. The title compound contains an unusual 1D ladder-like {V/As/O} chain with the phen ligand directly coordinated to the vanadium arsenate skeleton. To the best of our knowledge, 1 represents the first example of 1D vanadium arsenate decorated with the directly coordinated organic ligands.
Keywords: Organic–inorganic hybrid; Vanadium arsenate; One-dimensional chain; Hydrothermal synthesis; Crystal structure;

A new metal–organic hybrid compound {[Fe(phen)(btc)(OH2)]2  · CH3CH2OH} n 1, has been solvatothermally synthesized and structurally characterized. Compound 1 exhibits a novel supramolecular framework which constructed by {[Fe(phen)(btc)(OH2)]2} dimers and the guest ethanol molecules.
Keywords: Metal–organic hybrid; Supramolecular framework; Solvatothermal synthesis; Crystal structure;

A novel noncentrosymmetric inorganic–organic hybrid compound, (CHP)2CdI4 (CHP=4-cyano-1-hydrogen pyridinium), has been synthesized and the structure contains randomly arrayed CHP cations with two possible orientations, which is stabilized via hydrogen-bonding interactions with isolated and perfectly packed CdI4 2− tetrahedrons, showing a moderate second harmonic generation (SHG) of about three times as large as that of KDP.
Keywords: Hybrid; Synthesis; Structure; Second harmonic generation;

The first macrocyclic oxamide complex with nanometric pores: synthesis and two-dimensional network structure of [(CuL)3(ClO4)2Mn] n by Ya-Qiu Sun; Jin-Lei Tian; Wen Dong; Guang-Ming Yang; Dai-Zheng Liao; Zong-Hui Jiang; Shi-Ping Yan (137-139).
A new macrocyclic oxamide coordination polymer [(CuL)3(ClO4)2Mn] n (1) (CuL, H2L=2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien) containing nanometric pores structure has been synthesized and structurally characterized.
Keywords: Nanometric pores; Macrocyclic oxamide complex; Polymers;

Reaction of the compartmental proligand H2 L 2 with Co(OAc)2 has given the trinuclear cobalt(II) complex [Co3 L 3 (OAc)2(NCS)2], 1, in which the trinuclear core is supported by two tridentate acetate bridges, one in μ-acetato-κO,κO;κO-bridging mode and the other in μ3-acetato-κO;κO;κO-bridging mode. Two of the cobalt atoms are six-coordinate and the third is five-coordinate. The crystal structures of 1 and the dinuclear Ni(II) complexes [Ni2(L 2 )(OAc)2(NCS)], 2, and [Ni2(L 2 )(OAc)2(MeOH)2][PF6] · MeOH, 3, are reported.
Keywords: Crystal structure; Trinuclear cobalt(II) complex; Dinuclear nickel(II) complexes;