Inorganic Chemistry Communications (v.13, #10)

Contents List (iii-xi).

Ferrocene-based sensor R was synthesized and characterized by spectroscopic methods. The optical, electrochemical and cation-sensing properties of receptor R are presented. Receptor R behaves as a selective multi-channel signaling chemosensor molecule for Hg2+ and Cu2+ ions in CH3CN. The binding mode of Hg2+ with R was determined by 13C NMR titration. Both optical and electrochemical methods were applied for the detection of cations in water sample. The characteristic fluorescence of R with the Cu2+ selective ON–OFF and the Hg2+ selective fluorescence bathochromic shift can be observed and the concept has been used to construct a combinational logic circuit at the molecular level.The ferrocene–pyrazole dyad selectively binds with Hg2+ and Cu2+ ions which associates with efficient multi-channel signaling and molecular-scale arithmetic.Display Omitted
Keywords: Chemosensor; Multi-channel signaling; Molecular-scale arithmetic and cation sensor;

The reaction between Cu(NO3)2·3H2O and a tetra-aza macrocycle, more specifically, cyclen in 1:1 MeCN–MeOH solvent mixture forms a Cu2+–cyclen coordination complex in situ, that has been reacted with an isopolyanion [W6O19]2− in a slow diffusion technique, resulting in the isolation of an ion-pair solid [Cu(cyclen)(MeCN)][W6O19] (1). Single crystal structural investigation on 1 shows a square pyramidal geometry around the metal centre (copper ion) with an axially bound MeCN solvent molecule. The title compound 1 is the first crystallographically characterized ion-pair compound, in which a transition metal coordination complex of a tetra-aza-crown ether (cyclen) has been associated with a polyoxometalate cluster anion. This communication deals with synthesis, spectroscopic, structural and electrochemical analyses of compound 1.Supramolecular association between a coordination complex cation [Cu(cyclen)(MeCN)]2+ and an isopolyanion [W6O19]2– results in the isolation of the title compound [Cu(Cyclen)(MeCN)[W6O19] (1). The POM cluster anion has been shown to play an important role in tuning the red-ox property of the associated copper coordination complex cation in compound 1.Display Omitted
Keywords: Polyoxometalate; Cyclen; Crystallography; Spectroscopy; Electrochemistry;

Hydrothermal syntheses, crystal structures and characterizations of two new metal-fluorides based on niobium and tantalum by Yuquan Feng; Zhaohui Meng; Qunzeng Huang; Dongfang Qiu; Hengzhen Shi (1118-1121).
Two novel metal-fluorides [H2N(C2H4)2NH2][NbOF5](1) and [H2N(C2H4)2NH2][TaF7](2) have been obtained by a two-step hydrothermal method and characterized by elemental analysis, IR, PXRD, EDS, TG analysis and single-crystal X-ray diffraction. X-ray diffraction reveals that both compounds exhibit the supramolecular architectures through the electrostatic interactions and hydrogen bonding interactions between protonated piperazine and anions. In the [NbOF5]2− of compound 1, the Nb atom moves from the center of the octahedron toward the oxide atom to form a short Nb=O bond and long terminal Nb–F bond. In compound 2, the Ta atom can be described as a pentagonal bipyramidal geometry coordinated by seven fluorine atoms. Furthermore, the UV spectra in solid state of compounds 1 and 2 have also been discussed, which shows both of them have strong absorption bands.Two novel niobium and tantalum-containing fluorides [H2N(C2H4)2NH2][NbOF5] (1) and [H2N(C2H4)2NH2][TaF7] (2) by means of the hydrothermal method, and structural characterization by elemental analyses, IR, UV, EDS analysis, powder X-ray diffraction, TG analysis and X-ray single-crystal diffraction.Display Omitted
Keywords: Hydrothermal synthesis; Niobium-oxyfluoride; Tantalum-fluoride; EDS analysis;

A sensitive Schiff-base fluorescent indicator for the detection of Zn2+ by Lina Wang; Wenwu Qin; Weisheng Liu (1122-1125).
A Schiff-based fluorescence probe benzene-1,2-dicarbaldehyde bis-benzoyl hydrazide (L) was designed and synthesized. Its sensing behavior toward metal ions has been investigated by absorption and fluorescence spectroscopy. Indicator L showed high selectivity to Zn2+ in various solvents, whereas other metal ions failed to induce response. Especially Cd2+, which has similar chemical properties with Zn2+, can be distinguished from Zn2+ obviously.One Schiff-based fluorescence probe L was synthesized by an easy process. Spectroscopic studies exhibited that L showed highly selectivity to Zn2+, whereas other metal ions, including Cd2+, failed to respond.Display Omitted
Keywords: Zn2+; Chemosensor; Fluorescence; Selectivity; Schiff-base derivative;

Coordination assemblies of CdII/ZnII/CoII with the 3-(pyridin-4-yl) benzoate tecton: Structural diversity and properties by Dong-Sheng Li; Long Tang; Feng Fu; Miao Du; Jun Zhao; Ni Wang; Peng Zhang (1126-1130).
Display Omitted
Keywords: Coordination framework; Supramolecular clasp; Helical tubular; Fluorescence;

The reactions of MII nitrate (M = Co, Ni) with 1, 4-bis(imidazol-1-ylmethyl) benzene (bix) gave two novel interesting coordination networks [M2(bix)3(NO3)4]. The network contains 1D zigzag molecular ladder motifs, with anionic co-ligand NO3 as side arms on both sides, which thread through the squares of adjacent polymeric units in a mutual relationship, resulting in the first 1D→2D polythreading with finite components based on flexibly long ligand.The first 1D→2D polythreading with finite components based on flexibly long ligand was hydrothermally synthesized and the diffuse reflectance UV–vis spectrum suggests that they may be excellent candidates for potential photoactive materials.Display Omitted
Keywords: Coordination polymer; 1D→2D; Crystal structure; Polythreading with finite components;

A chiral tetranuclear cubane-like [Ni4O4] complex: Synthesis, structure and low-temperature magnetic behavior by Qing Liang; Rong Huang; Xiaodan Chen; Zhongshu Li; Xiangyang Zhang; Baiwang Sun (1134-1136).
A tetranuclear cubane-like [Ni4(EtOH)3L4] (H2L = (s)-2-((1-hydroxy-3-methylbutan-2-ylimino)methyl)phenol) complex has been prepared by the reaction of nickel(II) acetate with chiral Schiff base compound H2L. The X-ray crystal structure analyses revealed that the core of the cube was formed by four Ni(II) ions and four alkoxide oxygen atoms at alternating corners. The temperature (2–300 K) dependent magnetic susceptibility indicates it possesses a system with predominant ferromagnetic interaction.Using the chiral amino alcohol (l-Valinol) to prepare a Schiff base ligand (H2L) with salicylaldehyde is a simple but efficient approach to establish chiral and ploynuclear complexes. Combining H2L with transition metal salts, we synthesized a novel chiral tetranuclear complex [Ni4(EtOH)3L4] (1) and present its structure and magnetic properties.Display Omitted
Keywords: Chiral complex; Cubane-like; Nickel complexes; Schiff base; Magnetic properties;

[Pb2(boa)(Hbbp)2] has been synthesized by treating 4-carboxylphenoxyacetic (H2boa) and 2,6-bis(benzimidazolyl)pyridine (H2bbp) with metal salts under hydrothermal conditions. Adjacent metal centers forms dinuclear metal complex through carboxylato groups as building blocks. The arrangement of the half deprotonated H2bbp ligand and carboxylate groups exhibits a coordination gap around the Pb(II) ion, occupied possibly by a stereoactive lone pair of electrons on Pb(II), with the coordination environment around the lead atoms is hemidirected. This system is a particularly clear example that coordination sphere of a unique dinuclear Pb(II) compound was controlled by lone pair activity, weak Pb···O interactions, π–π stacking and the hydrogen bonds. The above weak interactions influence differently strong red-shifted effect about the solution and solid-state photoluminescence of the compound, compared to the free ligand.Hydrothermal conditions of Pb(NO3)2 with 4-carboxylphenoxyacetic (H2boa) and 2,6-bis(benzimidazolyl)pyridine (H2bbp) resulted in a unique dinuclear Pb(II) complex. Solution and solid state fluorescence properties of the Pb(II) complex were studied at room temperature, which exhibited strong red-shifted compared to the free ligand.Display Omitted
Keywords: Pb(II) complex; Weak Pb···O interaction; Lone pair; Hemidirected; Fluorescence;

Aggregation-induced emission of ruthenium(II) polypyridyl complex [Ru(bpy)2(pzta)]2+ by Yu Chen; Wen-Chao Xu; Jun-Feng Kou; Bo-Le Yu; Xu-Hui Wei; Hui Chao; Liang-Nian Ji (1140-1143).
A new ruthenium(II) complex [Ru(bpy)2(pzta)]2+ (1) [bpy = 2,2′-bipyridine; pzta = 6-(pyrzin2-yl)-1,3,5-triazine-2,4-diamine] has been synthesized and characterized. This complex exhibits a typical aggregation-induced emission (AIE) behavior that it is faint in solution but intense in the aggregate state.A new ruthenium(II) complex [Ru(bpy)2(pzta)]2+ was found to exhibit aggregation-induced emission (AIE) behavior.Display Omitted
Keywords: Ru(II) complexes; Polypyridine; Aggregation-induced emission; Crystal structure;

Synthesis, crystal structure and self-assembly property of a mixed (phthalocyaninato) (porphyrinato) europium triple-decker complex by Jitao Lu; Daopeng Zhang; Hailong Wang; Jianzhuang Jiang; Xiaomei Zhang (1144-1147).
A mixed phthalocyaninato and porphyrinato triple-decker complex [Eu2(Pc)2(TClPP)] was synthesized and characterized by elemental analysis, FT-IR, UV, and X-ray structure determination. Its self-assembling properties in mixed chloroform/methanol solution were investigated by TEM, SEM and XRD techniques. Investigation revealing the availability of the single crystal, together with the molecular structure, renders it possible to investigate the formation mechanism as well as the molecular packing conformation of self-assembled nanostructures fabricated from this complex in a more confirmed manner.Introduction of four chlorine atoms onto the four meso-phenyl groups of the porphyrin ligand in [Eu2(Pc)2(TClPP)] complex induces a two-dimensional supramolecular structure depending on the C–H…Cl interaction among chlorine atoms of adjacent porphyrins leading to the formation of nano-structures with sheetlike morphology.Display Omitted
Keywords: Crystal structure; Porphyrin; Phthalocyanine; Self-assembly; Rare earth;

Interaction of copper(II) with N-substituted bis(2-pyridylmethyl)amine derivatives by Mihyun Kim; Cindy Mora; Young Hoon Lee; Jack K. Clegg; Leonard F. Lindoy; Kil Sik Min; Pierre Thuéry; Yang Kim (1148-1151).
Interaction of copper(II) with the N-substituted bis(2-pyridylmethyl)amine derivatives, (R)-N 1,N 1-bis(pyridine-2-ylmethyl)butane-1,2-diamine (L 1 ) and (R)-2-(bis(pyridin-2-ylmethyl)amino)butan-1-ol (L 2 ), has led to isolation of optically active [Cu(L 1 )Cl]PF6 (1) and [Cu(L 2 )Cl]ClO4 (2), respectively. The X-ray structures of (1) and (2) show that the copper is bound to all four heteroatoms of the respective ligands as well as to a chlorine atom in a distorted square pyramidal arrangement in which the three nitrogens of L 1 or L 2 occupy three positions of each basal plane while the fourth position is occupied by the chloro ligand; apical sites in each case are filled by the amine donor from the NH2-substituted butane arm in L 1 or the (protonated) alcohol oxygen of the 2-aminobutane-1-ol substituent in L 2 . To a first approximation the coordination geometry in 2 is distorted square pyramidal; however, the remaining (axial) site on each copper centre is involved in a long contact (2.96 Å) with a bound chloro ligand from an adjacent complex which connects individual complex units in a zigzag 1-D polymeric chain, so that the coordination geometry could also be seen as pseudo-octahedral. A temperature-dependent magnetic study revealed the presence of ferromagnetic exchange coupling between copper centres in the chain reflecting the orthogonal structure between the chloro-bridged copper(II) ions; in contrast, and as expected, the discrete complex 1 is magnetically dilute.Cu(II) interacts with (R)-N 1,N 1-bis(pyridine-2-ylmethyl)butane-1,2-diamine (L 1 ) and (R)-2-(bis(pyridin-2-ylmethyl)amino)butan-1-ol (L 2 ) to yield the optically active discrete [Cu(L 1 )Cl]PF6 (1) and zigzag polymeric [Cu(L 2 )Cl]ClO4 (2) complexes, respectively; the latter compound displays a ferromagnetic interaction between metal centres.Display Omitted
Keywords: Copper(II); Coordination polymer; X-ray structure; Optically active; Dipyridylamine; Magnetic properties;

The reaction of 1-aminoadamantane hydrochloride and divalent metal chloride in concentrated hydrochloric acid medium yields two unusual complexes containing protonated 1-aminoadamantane, (C10H18N)1+ 2[ZnCl4]2 (1), (C10H18N)1+ 2[MnCl4(H2O)2]2 (2a) and (C10H18N)1+ 2[MnCl4(D2O)2]2 (2b). Their crystal structures have been determined by X-ray crystallography. Both complexes contain molecular network of (C10H18N)+ cations and divalent metal chloride polyhedral anions (Mn and Zn site symmetry 2/m). Dielectric constants of both two organic–inorganic hybrid salts were measured at different temperatures and frequencies. Different structures lead to large discrepancy in the dielectric property measurements. In addition, thermal analysis of complex 2 was studied.Two novel organic–inorganic compounds (C10H18N)1+ 2[ZnCl4]2 (1) and (C10H18N)1+ 2[MnCl4(H2O)2]2 (2) were prepared. Compound 1 displays 1D chain structure, compound 2 displays 2D layer structure cross-linked by hydrogen bondings. Different structures lead to large discrepancy in the frequency dependence of the dielectric constant measurements.Display Omitted
Keywords: Protonated; Polyhedral; Dielectric constant; Discrepancy;

The chiral dinuclear tetraazadiphenol macrocyclic copper(II) complexes [Cu2([20]-DCHDC)(La)2] {H2[20]-DCHDC = 14,29-dimethyl-3,10,18,25-tetraazapentacyclo-[25,3,1,04,9,112,16,019,24]ditriacontane-2,10,12,14,16(32),17,27(31),28,30-decane-31,32-diol; La  = N3 (II), NCS (IV) or S2O3 2 (V)} has been synthesized and structurally characterized by elemental analysis, conductance, electronic and IR spectra as well as FAB-MS method. Crystal structure of [Cu2([20]-DCHDC)(N3)2]·2CH3OH (III) determined by X-ray crystallography reveal the two square pyramidal copper centers bridged by the two phenoxide oxygen atoms, with large Cu–O–Cu angles {100.88(10)°}.The dinuclear tetraazadiphenol macrocyclic copper(II) complexes [Cu2([20]-DCHDC)(La)2] (La  = N3 , NCS or S2O3 2 ) are prepared by reacting [Cu2([20]-DCHDC)Cl2]∙H2O with an aqueous solution of NaN3, NaSCN, or Na2S2O3. The stable monoclinic crystals, [Cu2([20]-DCHDC)(N3)2]∙2CH3OH (III) suitable for X-ray crystallography are grown from complex II solution on slow evaporation of solvent methanol.Display Omitted
Keywords: Tetraazadiphenolic macrocycle; Dinuclear copper(II) complex; Square pyramidal geometry; Monodentate azido ligand;

Reaction of Ru(bpy)2Cl2 ·2 H2O with 1,2-bis(trifluoroacetyl)hydrazine H2(adc-CF3) under basic conditions yields the dinuclear [(μ-adc-CF3){Ru(bpy)2}2]2+ ion which was isolated and crystallized for structure determination in the meso diastereoisomer form as the bis(hexafluorophosphate). The Ru ··Ru distance was determined at 5.029(1) Å, and the N–N bond length at 1.463(5) Å reveals a hydrazido(2−) form of the bridge, implying unchanged + II metal oxidation states. Besides bpy-based reduction, the cyclic voltammetric analysis revealed two oxidation waves with a (3+) intermediate. Spectroelectrochemistry demonstrated that this intermediate [(μ-adc-CF3){Ru(bpy)2}2]3+ with a comproportionation constant of K c  = 108.8 and an absorption at 1680 nm (ε = 9900 M-1  cm 1) is a mixed-valent species as evident most convincingly from the EPR parameters at g 1  = 2.239, g 2  = 2.065, g 3  = 1.891 (gav  = 2.101, Δg = g 1  −  g 3  = 0.348).The 1,2-bis(trifluoracetyl)hydrazido(2−) bridge can connect two [Ru(bpy)2] complex fragments at a distance of about 5 Å in the RuIIRuII and the RuIIIRuII states.Display Omitted
Keywords: Crystal structure; Hydrazido ligand; Near-infrared ruthenium; Spectroelectrochemistry;

A sodium boroxide containing an unusual Na4O4 ladder core by Sarah C. Cole; Martyn P. Coles; Peter B. Hitchcock (1163-1165).
The reaction of dimesitylborinic acid and sodium tert-butoxide in toluene afforded the partially deprotonated boroxide salt, [Na4(OB{mes}2)4(HOB{mes}2)2], which crystallized from hexane with a laddered Na4O4 motif containing a neutral, disubstituted borinic acid ligand.Reaction of dimesitylborinic acid with sodium tert-butoxide afforded the partially deprotonated boroxide salt, [Na4(OB{mes}2)4(HOB{mes}2)2], which crystallized with a laddered Na4O4 motif containing a neutral, disubstituted borinic acid ligand.Display Omitted
Keywords: Sodium salt; Ladder structure; Boroxide;

A novel unexpected oxovanadium(IV) complex, [VO(L)(Phen)] (H2L = 2-((2-hydroxynaphthalen-1-yl)-methyleneamino)-5-oxotetrahydrofuran-2-carboxylic acid, Phen = 1, 10-phenanthroline) (1), in which the L2– is an unexpected in situ generated lactone Schiff base ligand from the precursor of K2HL1 (K2HL1  = potassium 2-(((2-hydroxynaphthalen-1-yl)methylene)amino)pentanedioate), has been synthesized and structurally characterized. The DNA binding properties of 1 with calf thymus DNA (CT-DNA) have been investigated by fluorescence and circular dichroism (CD) spectra, results indicate that 1 can bind to CT-DNA via an intercalative mode.A novel unexpected oxovanadium(IV) complex with in situ generated lactone Schiff base ligand and 1,10-phenanthroline was synthesized and structurally characterized, its DNA-binding properties with calf thymus DNA were investigated by spectroscopy.Display Omitted
Keywords: Oxovanadium(IV) complex; Schiff base; In situ generated lactone ligand; Crystal structure; DNA-binding;

Annulated dinuclear palladium(II) phthalocyanine complex as an effective photo-oxidation catalyst for near-infrared region light by Takahisa Ikeue; Makoto Sonoda; Satoshi Kurahashi; Haruaki Tachibana; Daichi Teraoka; Tamotsu Sugimori; Kuninobu Kasuga; Makoto Handa (1170-1172).
An annulated dinuclear palladium(II) phthalocyanine complex (1) was synthesized and characterized. It was found that 1 worked as a photo-catalyst for the decomposition of 1,3-diphenylisobenzofuran (DPBF) in aerated toluene under the irradiation of the light in the near-infrared (NIR) region (λ > 780 nm).An annulated dinuclear palladium(II) phthalocyanine complex (1) was synthesized and characterized. It was found that 1 worked as a photo-catalyst for the decomposition of 1,3-diphenylisobenzofuran (DPBF) in aerated toluene under the irradiation of the light in the near-infrared (NIR) region (λ > 780 nm).Display Omitted
Keywords: Photo-oxidization; Near-infrared region light; Dinuclear palladium(II) phthalocyanine;

A novel one dimensional coordination polymer of Cd(II)-pyrazine-2,3-dicarboxylate with a new coordination mode of pyrazine-2,3-dicarboxylate ligand (pzdc), {[Cd(pzdc)(4-mim)(5-mim)2]·½H2O} n (1) (4(5)-methylimidazole = 4(5)-mim), has been synthesized and characterized by elemental, thermal analysis, IR spectrum and single crystal X-ray diffraction technique. In complex 1, the Cd(II) ion has a distorted octahedral geometry, in which the pzdc moiety acts as a bridging ligand. Linkage isomerism of the coordinated 4(5)-methylimidazole ligand was observed in 1. The two adjacent one-dimensional chains connected by interchain hydrogen bonds among the N-H groups of methylimidazoles and carboxylate oxygens of pzdc, leading to a three-dimensional framework. The hydrogen bonds account for the coexistence of two unique coordination forms of methylimidazoles in the same coordination sphere.A novel one dimensional coordination polymer of Cd(II)-pyrazine-2,3-dicarboxylate with a new coordination mode of pyrazine-2,3-dicarboxylate ligand (pzdc), {[Cd(pzdc)(4-mim)(5-mim)2]·½H2O} n (1) (4(5)-methylimidazole = 4(5)-mim), has been synthesized and characterized. The Cd(II) ion exhibits a distorted octahedral geometry and is coordinated by two oxygen and one nitrogen atoms from two pzdc and three nitrogen atom from three 4(5)-mim ligands. In 1, pzdc ligand exhibits a new coordination mode and linkage isomerism of the coordinated 4(5)-methylimidazole ligand was observed.Display Omitted
Keywords: Linkage isomerism; Coordination polymer; Pyrazine-2,3-dicarboxylate complex; Cadmium complex;

Two new 3d-4f complexes, [LnCo(3,5-pdc)2(3,5-Hpdc) (H2O)7]·H2O (Ln = Gd 2, La 3; 3,5-pdcH2  = pyridine-3,5-dicarboxylic acid), have been synthesized by the self-assembly of Ln(III) oxides, 3,5-pdcH2 and the template molecule [Co(3,5-pdc)(H2O)5]·H2O (1) under hydrothermal conditions. Heterometallic complexes 2 and 3 are isostructural with supracyclic units containing four Ln(III) ions and two Co(II) ions, in which Co(II) and Ln(III) are linked by the deprotonated 3,5-pdcH2 ligands in three kinds of bridging modes. The weak antiferromagnetic coupling of complex 2 and 3 imply that the large 3,5-pdc bridges with the greater separation ( > 7 Å) cannot lead to long range magnetic ordering, the strength of d n -f n exchange coupling increasing with decreases the size of the lanthanide ion.Two 2D 3d-4f complexes, [LnCo(3,5-pdc)2(3,5-Hpdc) (H2O)7]·H2O (Ln = Gd 2, La 3; 3,5-pdcH2  = pyridine-3,5-dicarboxylic acid)), have been synthesized and structurally characterized, supracyclic units containing four Ln(III) ions, two Co(II) ions and six 3,5-pdc, in which Co(II) and Ln(III) are linked by the deprotonated 3,5-pdcH2 ligands in three kinds of bridging modes.Display Omitted
Keywords: 3d-4f complex; Pyridine-3,5-dicarboxylic acid; Hydrothermal synthesis; Hydrogen bonds; Magnetic property;

Hydrothermal synthesis and crystal structure of the first Keggin polyoxometalate supported cadmium coordination complex by Yan Wang; Li-Na Xiao; Hong Ding; Feng-Qing Wu; Ling Ye; Tie-Gang Wang; Shu-Yun Shi; Xiao-Bing Cui; Ji-Qing Xu; Da-Fang Zheng (1184-1186).
The first Keggin polyoxometalate supported cadmium coordination complex has been hydrothermally synthesized and characterized by IR, UV-Vis, XPS, TG, XRD, elemental analysis and single-crystal X-ray diffraction analysis.Display Omitted
Keywords: Polyoxoanion supported coordination complex; Crystal structure; Hydrothermal; Cadmium;

Lead corrole complexes in solution: Powerful multielectron transfer reagents for redox catalysis by Wolfgang Schöfberger; Florian Lengwin; Lorenz M. Reith; Manuela List; Günther Knör (1187-1190).
The first observation of Pb(II)-complexes of corroles and their photoinduced oxidation to the corresponding Pb(IV)-derivatives is reported. These compounds display metal-centered redox chemistry in solution. Their potential for catalytic oxygen atom transfer processes is explored.The first observation of Pb(II)-complexes of corroles and their photoinduced oxidation to the corresponding Pb(IV)-derivatives is reported. These compounds display metal-centered redox chemistry in solution. Their potential for catalytic oxygen atom transfer processes is explored.Display Omitted
Keywords: Lead complexes; Metal-oxo species; Corroles; Charge transfer; Electron transfer; Photochemistry;

The ultrasonic reaction of Lawesson's reagent (2,4-bis(4-methoxyphenyl)-1,3-dithiadiphosphetane-2,4-disulfide, LR) with Ag(OAc) and Ph3P (triphenylphosphane) gave an Ag20 cluster {[Ag20(ArP(OEt)S2)6(ArPOS2)6(Ph3P)8]·2(OAc)·8(H2O)·(CHCl3)} (1) (Ar = 4-methoxyphenyl). The core of this cluster is an Ag-based propeller comprised of one triangle central axis and three distorted rectangle leaves. The bipodal and tripodal P/S-containing ligands were generated from in situ P–S bond cleavage and P–O bond formation process.The ultrasonic reaction of Lawesson's reagent (2,4-bis(4-methoxyphenyl)-1,3-dithiadiphosphetane-2,4-disulfide, LR) with Ag(OAc) and Ph3P (triphenylphosphane) gave an Ag20 cluster {[Ag20(ArP(OEt)S2)6(ArPOS2)6(Ph3P)8]·2(OAc)·8(H2O)·(CHCl3)} (1) (Ar = 4-methoxyphenyl). The core of this cluster is an Ag-based propeller comprised of one triangle central axis and three distorted rectangle leaves. The bipodal and tripodal P/S-containing ligands were generated from in situ P–S bond cleavage and P–O bond formation process.Display Omitted
Keywords: Silver(I) cluster; Lawesson's reagent; Crystal structure;

Coordination polymers [Hg(L 2 )Cl2] n (1) and {[Hg2(L 2 )Cl4](DMF)} n (2) have been assembled from Hg(II) chloride and a novel tripyridyltriazole tecton 3,4-bis(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole (L 2 ) in different solvent media. Both complexes have been characterized by IR, microanalysis, powder X-ray diffraction, and thermogravimetric analysis. Single crystal X-ray diffraction indicates that the L 2 ligands take the (η3, μ2) and (η4, μ3) binding modes in 1 and 2, respectively, which connect the Hg(II) centers to afford linear and ladder-like 1D arrays. Interestingly, complex 1 exhibits strong solid state fluorescent emission at room temperature due to the intraligand transitions, whereas complex 2 is non-fluorescent.This work demonstrates the solvent effect on assemblies, crystal structures, and fluorescent properties of two 1D Hg(II) coordination polymers with a versatile tripyridyltriazole tecton.Display Omitted
Keywords: Hg(II) coordination polymers; Tripyridyltriazole ligands; Solvent effect; Crystal structures; Fluorescent properties;

A series of asymmetric 2,6-bis(arylimino)pyridines with alkyl and halogen substitutients on different iminoaryl rings and corresponding iron (II) complexes ([2-(Ar1N = CCH3)-6-(Ar2N = CCH3)C5H3N]FeCl2, 3a3j) are synthesized and characterized. These Fe(II) complexes are highly active for ethylene oligomerization with high selectivity for linear α-olefins. The oligomer distributions can be tuned by the synergism of alkyl-steric effect and halogen electronic effect, and the production of C6–C16 can reach more than 80% with the highest selectivity being 87.5% for 3 g (Ar1  = 2-ethylphenyl, Ar2  = 2-fluorophenyl), which is 15–30% higher than that catalyzed by their methyl or fluoro-substituted symmetric counterparts.A series of asymmetric bis(arylimino) pyridyl iron complexes with alkyl and halogen substitutients on different iminoaryl rings of ligands are synthesized and characterized. These complexes were found to catalyze ethylene oligomerization with high activity and led to the augmentation of the more useful C6–C16 portion.Display Omitted
Keywords: Ethylene oligomerization; Fe complexes; Linear α-olefins; Asymmetric 2,6-bis(imino)pyridines;

Hydrothermal syntheses of two novel coordination polymers based on tetranuclear metal cluster constructed by 1,3,5-Tris(2H-tetrazol-5-yl)benzene ligand by Mei-Na Li; Guang-Sheng Yang; Shun-Li Li; Hong-Ying Zang; Guang-Juan Xu; Kui-Zhan Shao; Zhong-Min Su (1203-1206).
Two new coordination polymers, namely [Zn3(BTT)(μ 3-OH)3] (1), and [Mn3(BTT)(μ 3-OH)3] (2), where H3BTT = 1,3,5-Tris(2H-tetrazol-5-yl)benzene, have been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction. The structure of compound 1 can be described as tetranuclear zinc cluster linked with zinc (Zn2II) atoms to form a 2D layer, and the adjacent parallel layers bridged by the rigid H3BTT ligand to show 3D network. Taking Mn ions in replace of Zn ions, a new compound 2 is successfully obtained which is isostructural with 1. In addition, photoluminescent property for 1, magnetic properties for 2 and thermogravimetric analyses for 1 and 2 are investigated in detail.Two novel isostructural compounds, namely [Zn3(BTT)(μ 3-OH)3] (1), [Mn3(BTT)(μ 3-OH)3] (2) by combining polytetrazolate rigid ligand. The μ 3-OH group linked MII (Zn and Mn) atoms to form interesting 2D layers structure and the BTT bridged adjacent layers to give a 3D network with tetranuclear metal–oxygen clusters and 16-membered metallocycles.Display Omitted
Keywords: Coordination polymer; Hydrothermal synthesis; Tetrazolate ligand; Photoluminescent property;

A series of copper(II) complexes of the formula [Cu(L)(dppe)(N3)2] (1a3a) and [Cu(L)(dppe)(NCS)2] (1b–3b) (where L  = 4-(2′-thiazolylazo)chlorobenzene (L 1 ); 4-(2′-thiazolylazo)bromobenzene (L 2 ) and 4-(2′-thiazolylazo)iodobenzene (L 3 ); dppe =  cis-1,2-bis(diphenylphosphino)ethane) has been prepared and characterized on the basis of their elemental analysis, molar conductance, magnetic moment, IR, UV–vis and 1H NMR spectral studies. The electrochemical behaviour of the complexes showed that the redox responses of copper(II) complexes shifted to more negative potential in order of decrease in electron withdrawing nature of the substituent on the azo ligands. All the complexes exhibit intraligand (π→π*) fluorescence in blue-green region with high quantum yield in DMF solution.A series of copper(II)-azido/thiocyanato complexes with thiazolylazo dye and 1,2-bis(diphenylphosphino)ethane have been prepared and characterized by their elemental analyses, IR, UV–Vis and 1H NMR spectral studies All the complexes exhibit intraligand (π→π*) fluorescence with high quantum yield in DMF solution.Display Omitted
Keywords: Azo complexes; Spectral studies; Cyclic voltammetry; Photoluminescence; Properties;

Synthesis, structure and characterization of 1D threefold-bridging copper(II) chain with strong ferromagnetic coupling by Qiao-Juan Su; Shao-Hua Li; Li Wang; Cheng-Zhi Xie; Yan Ouyang; Jing-Yuan Xu (1210-1212).
A 1D chain Cu(II) complex: [Cu(2-Clnic)(μ 1,1-N3)(CH3OH)]n(1) (2-Clnic=2-chloronicotinate) has been synthesized and characterized by IR, elemental analysis, X-ray crystal diffraction and magnetic properties. Single-crystal structural analysis shows that complex 1 consists of 1D Cu(II) chains containing threefold bridging ligands, one μ 1,1-azido, one (syn–syn) 2-chloronicotinate and one methanol molecule. The magnetic susceptibilities of 1 has been investigated, indicating strong ferromagnetic interactions with J  = 81.22 cm−1.Use of 2-chloronicotinate, NaN3 with Cu(NO3)2·3H2O in methanol has enabled the synthesis of Cu(II) complex [Cu(2-Clnic)(μ1,1-N3)(CH3OH)]n∙ nCH3OH (1). Single-crystal structural analysis shows that complex 1 consists of 1D Cu(II) chains containing threefold bridging ligands, one μ1,1-azido, one (syn–syn) 2-chloronicotinate and one methanol molecule. Magnetic studies reveal that the compound has strong ferromagnetic interactions with J  = 81.22 cm−1.Display Omitted
Keywords: Copper complex; Azide; 2-chloronicotinate; Ferromagnetic property;

3-Carbaldehyde-chromone semicarbazone (L) and its Cu(II), Zn(II), Ni(II) complexes were synthesized and characterized on the basis of crystal structure and other structural characterization methods. The metal ions and Schiff base ligand can form mononuclear five-coordination complexes with 1:1 metal-to-ligand stoichiometry at the metal ions as centres. The transition metal complexes may be used as potential anticancer drugs, because they bind to calf thymus DNA via an intercalation binding mode with the binding constants at the order of magnitude 105–106  M− 1, and the metal complexes present stronger DNA binding affinities than the free ligand alone. In addition, the antioxidant activities of the ligand and its metal complexes were investigated through scavenging effects for superoxide anion and hydroxyl radical in vitro, indicating that the compounds show stronger antioxidant activities than some standard antioxidants, such as mannitol and vitamin C.The transition metal ions and Schiff base ligand can form mononuclear five-coordination complexes with 1:1 metal-to-ligand stoichiometry at the metal ions as centres. Their biological activities, such as DNA binding properties and antioxidant activities were investigated systematically.Display Omitted
Keywords: Transition metal complexes; Schiff base ligand; Crystal structure; DNA binding properties; Antioxidant activities;

A novel polyoxometalate tri-supported mixed-valent transition metal coordination complex by Li-Na Xiao; Yan Wang; Yan Chen; Yu Peng; Guo-Dong Li; Xiao-Bing Cui; Shu-Yun Shi; Tie-Gang Wang; Zhong-Min Gao; Ji-Qing Xu (1217-1220).
A new compound [Mo8V7O42][Cu(2,2′-bpy)2]2[Cu(2,2′-bpy)]·2H3O (1) has been synthesized under hydrothermal conditions and characterized by IR, UV–vis spectrum, elemental analysis, XRD, ESR, XPS, X-ray diffraction analysis and magnetic property study. Single-crystal X-ray structure analysis indicates that the compound 1 is a novel Keggin polyoxoanion tri-supported mixed-valent transition metal coordination complex.The first Keggin polyoxometalate supported mixed-valent transition metal coordination complex has been hydrothermally synthesized and characterized by IR, XPS, XRD, ESR, UV–vis, elemental analysis, single-crystal X-ray diffraction analysis and magnetic property study.Display Omitted
Keywords: Polyoxometalates; Supported; Hydrothermal synthesis; Keggin; Hydrogen bonds;

A novel hexagonal-based honeycomb compound with overall formula {[KCr(C2O4)3][Cu(pypn)(H2O)](H2O)4} is reported in which pypn is with the tetradentate ligand (N,N′-bis(2-pyridylmethyl)-1,3-propanediamine). The [KCr(C2O4)3]2− moiety forms a hexagonal honeycomb structure, while the five-coordinated [Cu(pypn)(H2O)]2+ moiety is located in between the layers, partly filling the holes in the cavities. The synthesis, X-ray crystal structure and some spectroscopic properties are presented. The coordination of Cr(III) is octahedral, with a CrO6 chromophore, and the K+ ion is in a KO6 environment (K–O distances vary from 2.36 to 2.48 Ǻ). The [KCr(C2O4)3]2− layers have the K+ ions in a Λ conformation, while the Cr(III) ions in the Δ conformation. The geometry around the Cu(II) is five-coordinated with four nitrogens from the chelating pypn ligand in a plane and the apical position being occupied by the oxygen atom of the coordinating water molecule. The packing of the cationic and the anionic layers appears to be of special interest.A layer compound consisting of anionic bimetallic species [KCr(C2O4)3](2−) is reported. The layers are separated by Cu(II)-tetraamine cations.Display Omitted
Keywords: Copper; Chromium; Honeycomb structure; Hydrogen bond;