Inorganic Chemistry Communications (v.13, #2)

Contents List (iii-x).

The new amino-phosphinite chiral ligand 1 has been synthesized and the corresponding more stable oxide has been characterized by X-ray analysis. The ligand 1 behavior has been studied in the styrene hydroformylation using [Rh(acac)(CO)2] and [Rh(COD)2]BF4 as precursors. With both pre-catalysts, in mild catalysis conditions, the branched aldehyde 2-phenylpropanal was obtained with high yield and regioselectivity but as a racemic mixture.The new amino-phosphinite chiral ligand (Sa )-4-((S)-1-(diphenylphosphinooxy)-3-methylbutan-2-yl)-4,5-dihydro-3H-dinaphtho[2,1-c:1′,2′-e]azepine (1) has been synthesized and the corresponding more stable oxide has been characterized by X-ray analysis. The ligand behavior in styrene hydroformylation using [Rh(acac)(CO)2] and [Rh(COD)2]BF4 as precursors has been studied. With both pre-catalysts, branched aldehyde 2-phenylpropanal was obtained in mild catalysis conditions with high yield and regioselectivity but as racemic mixture, indicating the loss of the ligand (1) during catalytic run. To support these results, the reactions of [Rh(acac)(CO)2] and [Rh(COD)2]BF4 with the ligand 1 have been performed and the pre-catalysts behavior under CO/H2 has been investigated.
Keywords: Chiral amino-phosphinite; Hemilabile ligand; Catalysis; Hydroformylation; X-ray structural determination;

Solvothermal treatment of ZnNO3, NaN3 and 4-[2H7]methylbenzonitrile at 125 °C for 2 days produced a 2D metal–organic framework [Zn(4-MPTZ-[2H7])2] (1) with a hexagonal net.Under hydrothermal conditions, NaN3, 4-[2H7]methylbenzonitrile, reacted with Zn(NO3)2 to give a 2D layered network complex [Zn(4-MPTZ-[2H7])2] (1) [4-MPTZ = 5-(4-methylphenyl)tetrazole]. Single crystal X-ray determination shows that complex 1 consists of two Zn atoms and six tetrazolyl ligands in the crystallographically asymmetric unit with orthorhombic space group Pbcn, each Zn center is linked to three other Zn centers through the bridging ligands. And the dielectric constants of 1 were measured at different temperature, and deuterated effect at the lowest frequency (104  Hz) can be estimated to increase 33% at 290 K which was never seen before in the isotope effect.
Keywords: Zn(II); Coordination polymer; Fluorescence; Permittivity;

Schiff base (L) obtained by reacting 2-methylthiobenzeldehyde with 2-(phenylseleno)ethylamine on reaction with di-μ-chlorobis{η6-benzene)dichloro ruthenium(II)}(a) forms [Ru(L)2][PF6]2 (1) when L:a  = 4:1 and stirring time of reactants 8 h whereas for L:a  = 2:1 and stirring time 1 h the complex formed is [Ru(η6-C6H6)(L)][PF6]2 (2). The geometry around Ru in complex 1 is distorted octahedral. The 2 exhibits the pseudo-octahedral half sandwich “piano-stool” disposition around Ru. The Ru–Se distances are 2.4683(10)–2.4683(10) Ǻ. The 2 shows high catalytic activity for oxidation of alcohols (TON upto 9.6 × 104).Schiff base (L) synthesized by reacting 2-methylthiobenzeldehyde with 2-(phenylseleno)ethylamine on reaction with di-μ-chlorobis{η6-benzene)dichloro-ruthenium(II)}(a) forms two type of species: (i) [Ru(L)2][PF6]2 (1) [L:a  = 4:1 and reaction time ∼8 h] and (ii) [Ru(η6-C6H6)(L)][PF6]2 (2) [L:a  = 2:1 and reaction time ∼1 h]. This is first example in which chloro as well benzene ring both are successively substituted by controlling metal:ligand ratio and duration of reaction. The geometry around Ru in complex 1 is distorted octahedral. The 2 has a pseudo-octahedral half sandwich “piano-stool” disposition of ligands around Ru. The Ru–Se distances are 2.4683(10)–2.5082(7) Ǻ. The proton and carbon-13 NMR spectra of L and its both complexes 1 and 2 authenticate them. The 2 shows high catalytic activity for oxidation of primary and secondary alcohols both (TON upto 9.6 × 104; TOF upto 4.80 × 104  h−1).
Keywords: Selenated Schiff base; Half sandwich complex; Ruthenium(II); Crystal structure; Catalytic oxidation; Alcohols;

A flexible hydroxy-bridged dicopper complex as catechol oxidase mimic by Tamás Csay; Balázs Kripli; Michel Giorgi; József Kaizer; Gábor Speier (227-230).
The molecular structure of [Cu2(4′MeInd)2(MeOH)(μ-OH)]ClO4·MeOH [4′MeIndH = 1,3-bis(4′-methyl-2-pyridylimino)isoindoline] was fully determined by IR, UV–Vis, and X-ray crystal analysis. With the flexible hydroxy-bridged isoindoline-containing dicopper complex has been shown that it does not maintain its dimeric nature when catalyzing catechol oxidase-like reaction.A flexible hydroxy-bridged dicopper complex with isoindoline ligand has prepared and characterized and shown that it does not maintain its dimeric nature when catalyzing catechol oxidase-like reaction.
Keywords: Copper; Oxidation; Catechol; Catecholase mimics;

The paper presents a combined experimental and computational study of Re(III) complexes containing 2-benzoylpyridine (bopy). Two novel complexes [ReX3(bopy)(PPh3)] (X = Cl, Br) have been obtained in the reactions of [ReX3(MeCN)(PPh3)2] with 2-benzoylpyridine in dichloromethane and have been studied by IR, UV−Vis spectroscopy and X-ray crystallography. The electronic structure of [ReCl3(bopy)(PPh3)] has been calculated with the density functional theory (DFT) method. The spin-allowed electronic transitions of [ReCl3(bopy)(PPh3)] have been calculated with the time-dependent DFT method and the UV–Vis spectrum has been discussed on this basis.The paper presents a combined experimental and computational study of Re(III) complexes containing 2-benzoylpyridine (bopy). Two novel complexes [ReX3(bopy)(PPh3)] (X = Cl, Br) have been obtained in the reactions of [ReX3(MeCN)(PPh3)2] with 2-benzoylpyridine in dichloromethane and have been studied by IR, UV–Vis spectroscopy and X-ray crystallography. The electronic structure of [ReCl3(bopy)(PPh3)] has been calculated with the density functional theory (DFT) method. The spin-allowed electronic transitions of [ReCl3(bopy)(PPh3)] have been calculated with the time-dependent DFT method and the UV–Vis spectrum has been discussed on this basis.
Keywords: Rhenium(III) complexes; 2-Benzoylpyridine; X-ray structure; Electronic structure; DFT calculations;

Fe(II) porphyrazine/resin exhibits good catalytic performance, and photocatalytic degradation of RhB in the presence of Fe(II) porphyrazine/resin was performed at different conditions.The novel tetra-(1,4-dithiin) metal-free (H2Pz) and metalloporphyrazines (MPz, M = Mg, Fe) bearing peripheral tetrapropyl-bromine derived from 2,3-dicyano-5-propyl-bromine-1,4-dithiin, were synthesized in a multi-step reaction sequence. These complexes were characterized by 1H NMR, IR, UV–vis, GC–MS, XPS and elemental analysis and their UV–vis spectra were discussed in detail. The iron(II) tetra-(1,4dithiin)porphyrazine bearing peripheral tetrapropyl-bromine was supported on an Amberlite CG-400 resin to form a biomimetic catalyst, the ability of which for activating O2 and H2O2 was estimated from the degradation of Rhodamine B (RhB) under visible light irradiation (λ  ⩾ 420 nm). More than 70% of the RhB was degraded by O2 in air for 24 h in the solution of pH 9.18 and by H2O2 only for 12 h in the solution of pH 3.0.
Keywords: Sulfur-containing porphyrazine iron(II); Synthesis; Activating molecular oxygen; Biomimetic catalyst; Photodegradation;

Synthesis, crystal, luminescent properties and electronic structures of two copper(I) halide polymers based on Cu4I4 cubane tetramers by Xiaochuan Chai; Shuai Zhang; Yiping Chen; Yanqiong Sun; Hanhui Zhang; Xianglan Xu (240-243).
Two coordination polymers [Cu4I4(en)2] n 1 and [Cu4I4(pn)2] n 2 containing Cu4I4 cubane tetramers were prepared. Compound 1 displays a 3D framework and 2 possesses a 2D layer, respectively.Two novel coordination polymers [Cu4I4(en)2] n 1 and [Cu4I4(pn)2] n 2 (en = 1,2-diaminoethane and pn = 1,3-diaminopropane) were prepared by hydrothermal methods and determined by single-crystal X-ray diffraction analysis. Compound 1 possesses a 3D zeolite-like architecture with infinite intersected channels, constructing from cubane Cu4I4 tetramers, which is simplified into a twofold interpenetrating dia network. Compound 2 with the similar Cu4I4 cores, features a 2D layer with parallelogram-shaped channels along the b axis, showing a uninodal sql net. Both exhibit luminescent emission bands at about 600 nm at room temperature when excited at 350 and 370 nm, respectively. Furthermore, thermogravimetric analyses, optical diffuse reflectance spectroscopy, and the theoretical calculations were discussed.
Keywords: Copper(I) halide polymers; Luminescent emission; Optical diffuse reflectance spectroscopy; Electronic structures;

Polyoxometalate–molybdenylacetylacetonate hybrid complex: A reusable and efficient catalyst for oxidation of alkenes with tert-butylhydroperoxide by Majid Moghadam; Valiollah Mirkhani; Shahram Tangestaninejad; Iraj Mohammadpoor-Baltork; Maedeh Moshref Javadi (244-249).
The hybrid complex consist of molybdenylacetylacetonate complex covalently linked to a lacunary Keggin-type polyoxometalate, was synthesized and characterized by elemental analysis, SEM, diffuse reflectance UV–Vis and FT-IR spectroscopic methods. The hybrid complex, [MoO2(acac)–POM], was used for alkene epoxidation with tert-BuOOH in 1,2-dichloroethane as solvent. This heterogeneous catalyst was reused several times in the oxidation of cyclooctene.The hybrid complex consist of molybdenylacetylacetonate complex covalently linked to a lacunary Keggin-type polyoxometalate, K8[SiW11O39] (POM), was synthesized and characterized by elemental analysis, SEM, XRD, diffuse reflectance UV–Vis and FT-IR spectroscopic methods. The hybrid complex, [MoO2(acac)–POM] (1), was used for alkene epoxidation with tert-BuOOH in 1,2-dichloroethane as solvent. The complex (1) can catalyze epoxidation of various olefins including non-activated terminal olefins. The effect of reaction parameters such as oxidant, solvent, and temperature on the epoxidation of cyclooctene was also investigated. This heterogeneous catalyst was reused several times in the oxidation of cyclooctene.
Keywords: MoO2(acac)2; Polyoxometalate; Olefin oxidation; tert-BuOOH; Hybrid compound;

Hydrothermal syntheses, structures and luminescent properties of group IIB metal coordination polymers based on bifunctional 1H-tetrazolate-5-acetic acid ligand by Mei-Feng Wu; Fa-Kun Zheng; Gang Xu; A-Qing Wu; Yan Li; Hui-Fen Chen; Sheng-Ping Guo; Feng Chen; Zhi-Fa Liu; Guo-Cong Guo; Jin-Shun Huang (250-253).
Three new group IIB metal coordination polymers based on tza2− ligand were obtained under different reaction conditions, which indicates that reaction temperature and metal centers play important roles in construction of final metal-organic frameworks.Hydrothermal reaction of 1H-tetrazolate-5-ethyl acetate (Htzea), MCl2 (M = Zn, Cd) and NaOH at different reaction temperatures produced three new coordination polymers: 2-D layered polymer [Zn(tza)(H2O)2] n 1, and 1-D chained supramolecular isomers 2 and 3 formulated as [Cd(tza)(H2O)2] n (H2tza = 1H-tetrazolate-5-acetic acid), respectively. In these obtained polymers, tza2− ligand adopts variable coordination modes: μ 3-κN3:κO1:κO2,N1 and μ 3-κN1:κN3:κO2 for 1, and μ 3-κN2:κN1,O2:κO1,O2 for 2 and 3. The effects of reaction temperature and metal centers on the final polymeric frameworks have been discussed. Polymers 13 exhibit blue photoluminescence mainly arising from intraligand transitions of tetrazolate rings in tza2− ligand.
Keywords: 1H-Tetrazolate-5-acetic acid; Coordination polymer; Crystal structure; Supramolecular isomer;

Reactions of Hpytza (Hpytza = 5-(2-pyridyl)tetrazole-2-acetic acid) with ZnCl2 or CdCl2 under hydrothermal conditions, produced two new compounds, [Zn(pytza)2(H2O)2] (1) and [CdCl(pytza)] n (2). Compound 1 is mononuclear while compound 2 shows a two-dimensional network. Furthermore, the luminescence properties of 1 and 2 were investigated at room temperature in the solid state.Reactions of Hpytza (Hpytza = 5-(2-pyridyl)tetrazole-2-acetic acid) with ZnCl2 or CdCl2 under hydrothermal conditions, produced two new compounds, [Zn(pytza)2(H2O)2] (1) and [CdCl(pytza)] n (2). Both compounds were structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. Compound 1 is mononuclear while compound 2 shows a two-dimensional network. Furthermore, the luminescence properties of 1 and 2 were investigated at room temperature in the solid state.
Keywords: Zn(II); Cd(II); 5-(2-Pyridyl)tetrazole-2-acetic acid; Crystal structure; Luminescence;

A new family of tripodal ligands based on diazafluorene and corresponding trinuclear Ru(II) complexes have been prepared. These complexes exhibit MLCT absorption around 410 nm and emission at around 582 nm. Cyclic voltammetry of these complexes comprise one Ru(II)-centered oxidation and three ligand-centered reduction processes.Four tripodal ligands 2,2′,2″-tris[4-(4,5-diazafluoren-9-ylhydrazinyl)methylenephenoxyethyl]amine (L1), 1,1,1-tris[4-(4,5-diazafluoren-9-ylhydrazinyl)methylenephenoxymethyl]propane (L2), 1,3,5-tris[4-(4,5-diazafluoren-9-ylhydrazinyl)methylenephenoxymethyl]-2,4,6-trimethylbenzene (L3), 1,3,5-tris[4-(4,5-diazafluoren-9-ylhydrazinyl)methylenephenoxymethyl]benzene (L4), and corresponding Ru(II) complexes [(bpy)6L1–4(RuII)3](PF6)6 (Ru-L1–4) have been synthesized. Cyclic voltammetry of these complexes comprise one Ru(II)-centered reversible oxidation and three ligand-centered reductions. Photophysical behaviors are investigated by UV–Vis absorption and luminescence spectrometry. These complexes display metal-to-ligand charge transfer absorption at around 410 nm and emission at around 582 nm.
Keywords: Trinuclear Ru(II) complex; UV–Vis absorption; Emission; Electrochemistry;

A novel 2-D coordination polymer with yellow fluorescence constructed from mixed ligands and mixed-valence Cu(I/II), [ Cu 4 I Cu II ( sip ) 2 ( bipy ) 4 ( H 2 O ) 2 ] n was synthesized and characterized by IR spectra, TGA, XPS, EPR and single-crystal X-ray diffraction. It exhibits a 2-D layer-like framework constructed from {Cu(1)} n and {Cu(2)–Cu(3)} n chains, in which four-coordinated CuII and three-coordinated CuI environments are observed.A new 2-D inorganic–organic hybrid constructed from mixed-valence Cu(I/II) ions and mixed ligands, [ Cu 4 I Cu II ( sip ) 2 ( bipy ) 4 ( H 2 O ) 2 ] n (H3sip = 5-sulfoisophthalic acid, bipy = 4,4′-bipyridine), has been synthesized and characterized by IR, TGA, XPS, EPR and single-crystal X-ray diffraction. Two different kinds of chains in the compound constructed from [CuO4] planar squares and [CuN2O] triangulars, respectively, further interconnect together to give rise to an interesting 2-D layer framework. The compound exhibits strong yellow emission at 445 nm excited by 378 nm in the solid state at room temperature.
Keywords: Inorganic–organic hybrid; Mixed-valence Cu(I/II); 2-D layer; Hydrothermal synthesis; Crystal structure; Photoluminescence;

Copper(II) complexes with 15- and 16-membered diaza dioxa Schiff-base macrocyclic ligands “[Cu(R[15 or 16]N2O2)]2+ (R = Et, Pr, Ph, Ch)” were entrapped in the nanopores of zeolite-Y by a three-step process in the liquid phase: (i) exchange of Cu(II) ions with NaY in water solution, (ii) reaction of Cu(II)–NaY with excess 1,3-bis(2-carboxyaldehydephenoxy)propane (O2O2) in methanol; [(1,3-bis(2-carboxyaldehydephenoxy)propane)copper]2+@NaY, [Cu(O2O2)]2+@NaY (iii) template synthesis of [Cu(O2O2)]2+@NaY with diamine. The new complex nanoparticles encapsulated within nanopores of zeolite Y have been characterized by FT-IR, DRS, XPS, TGA, UV–vis spectroscopic techniques, X-ray diffraction (XRD) and elemental analysis as well as nitrogen adsorption.Copper(II) complexes with 15- and 16-membered diaza dioxa Schiff-base macrocyclic ligands “[Cu(R[15 or 16]N2O2)]2+ (R = Et, Pr, Ph, Ch)” were entrapped in the nanopores of zeolite-Y by a three-step process in the liquid phase: (i) exchange of Cu(II) ions with NaY in water solution, (ii) reaction of Cu(II)–NaY with excess 1,3-bis(2-carboxyaldehydephenoxy)propane (O2O2) in methanol, [(1,3-bis(2-carboxyaldehydephenoxy)propane)copper]2+@NaY, [Cu(O2O2)]2+@NaY (iii) template synthesis of [Cu(O2O2)]2+@NaY with diamine. The obtained new complex nanoparticles entrapped in the nanopores of zeolite Y have been characterized by elemental analysis FT-IR, XPS, DRS, UV–vis spectroscopic techniques, molar conductance, magnetic moment data, XRD and nitrogen adsorption. Analysis of data indicates all of the complexes have been encapsulated within nanopores without affecting the zeolite framework structure.
Keywords: Complex nanoparticles; Zeolite encapsulation; Copper(II); Nanocomposite materials;

In cis-(CO)-trans-(Cl)-[Ru(SRaaiNR)(CO)2Cl2] the SRaaiNR (1-alkyl-2-{(o-thioalkyl)phenylazo}imidazoles) acts as N(imidazole) (N), N(azo) (N′) bidentate chelator while in trans-(Cl)-[Ru(SRaaiNR)(CO)Cl2] it is NN′S tridentate ligand. Electronic structure, spectral and redox properties of the complexes have been explained by the DFT and TDDFT computations.The complexes, cis-(CO)-trans-(Cl)-[Ru(SRaaiNR)(CO)2Cl2] (2) and trans-(Cl)-[Ru(SRaaiNR)(CO)Cl2] (3) (SRaaiNR = 1-alkyl-2-{(o-thioalkyl)phenylazo}imidazoles; R = Me (1a) and Et (1b)) have been synthesized and characterized. The structural confirmation is achieved by single crystal X-ray structure determinations. The complexes show Ru(III)/Ru(II) couple and ligand reductions. Electronic structure and spectral properties of the complexes have been explained with the DFT and TDDFT calculation.
Keywords: Ruthenium-carbonyl; Thioarylazoimidazoles; X-ray structure; Electrochemistry; DFT calculation;

Crystal structure and magnetic property of a 3D heterometallic coordination polymer constructed by 3-cyanobenzoate and 3-(5H-tetrazol) benzoate ligands by Feng Chen; Fa-Kun Zheng; Guang-Ning Liu; A-Qing Wu; Ming-Sheng Wang; Sheng-Ping Guo; Mei-Feng Wu; Zhi-Fa Liu; Guo-Cong Guo; Jin-Shun Huang (278-281).
A novel heterometallic Cd(II)/Co(II) coordination polymer based on 3-cyanobenzoate and 3-(5H-tetrazol)benzoate ligands features a 3D open framework encapsulating 1D chiral channels, exhibiting antiferromagnetic interactions.Hydrothermal reaction of Cd(NO3)2, Co(NO3)2, Na(3-cba) and NaN3 yielded a 3D heterometallic coordination polymer, [Cd(μ5-3-tzba)(μ2-3-cba)(μ3-OH)Co(H2O)] n ·2nH2O 1 (3-H2tzba = 3-(5H-tetrazol)benzoic acid and 3-Hcba = 3-cyanobenzoic acid), which was characterized by single-crystal X-ray diffraction. The in situ [2 + 3] cycloaddition reaction of nitrile and azide in presence of Cd(II) salt afforded tetrazolate-based 3-tzba2− ligand. In 1, metal-oxo chains [Cd(μ3-OH)Co] n are linked by 3-tzba2− in an unprecedented μ5-κN1:κN2:κN3:κN4:κO1,O2 coordination mode to form 2D layers, which are further pillared by 3-cba to generate a 3D open framework encapsulating 1D chiral channels. Variable-temperature magnetic studies show that 1 exhibits antiferromagnetic interactions between Co(II) ions bridged by μ3-OH group.
Keywords: 3-Cyanobenzoate complex; Tetrazolate complex; Hydrothermal synthesis; Crystal structure; Magnetic property;

Solvothermal treatment of BaCl2 and 2-(4-(1H-tetrazol-5-yl)pyridinium-1-yl) acetate at 80 °C for 96 h produced the first deca-coordinated Ba(II)-tetrazole complex [Ba(4-TPA)2(H2O)4·3.5(H2O)] n  (1) in which [BaO2] n chain acts as inorganic skeleton. The compound 1 shows interesting dielectric constant properties at a relatively high frequency of 1 M Hz.The first 1D Ba(II)-tetrazole coordination polymer, [Ba(4-TPA)2(H2O)4·3.5(H2O)] n (1), which is constructed by a [BaO2] n inorganic skeleton chain with organic 4-TPA wings on both sides, has been synthesized and characterized by single crystal X-ray crystallography and temperature dependence dielectric constant (ε) measurement, (4-TPA = 2-(4-(1H-tetrazol-5-yl)pyridinium-1-yl) acetate). The ε of single crystal sample is almost twice the ε of powder sample. However, the dielectric loss of the crystal is relatively smaller, which is attributed to the highly ordered arrangement in crystal lattice.
Keywords: Ba(II) complex; Metal-organic framework; Dielectric constant; Ordered arrangement; Ba–O skeleton;

Six isomorphous metal–organic frameworks: M2(ATPA)3(DMF)2(H2O)2 (M = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6); ATPA = 2-aminoterephthalate, DMF = N,N-dimethylformamide), were synthesized by the self-assembly of lanthanide ions, 2-aminoterephthalate, DMF and H2O. Their crystal structures determined by X-ray crystallography reveal interpenetrating frameworks. Compounds 2, 3, 5 and 6 exhibit mainly ligand luminescence at room temperature while 3 exhibits enhanced Eu3+ emissions at 77 K. Magnetic studies indicate 4 is paramagnetic with slight Gd3+–Gd3+ couplings.Six isomorphous metal–organic frameworks: M2(ATPA)3(DMF)2(H2O)2 (M = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6); ATPA = 2-aminoterephthalate, DMF = N,N-dimethylformamide), were synthesized by the self-assembly of lanthanide ions, 2-aminoterephthalate, DMF and H2O. Their crystal structures determined by X-ray crystallography reveal interpenetrating frameworks. Compounds 2, 3, 5 and 6 exhibit mainly ligand luminescence at room temperature while 3 exhibits enhanced Eu3+ emissions at 77 K. Magnetic studies indicate 4 is paramagnetic with slight Gd3+–Gd3+ couplings.
Keywords: Metal–organic frameworks; 2-Aminoterephthalate; Lanthanide; Luminescence; Magnetic;

A novel 3D silver(I) coordination polymer exhibiting unprecedented μ3- and μ4-bonding modes of 2-aminopyrazines by Di Sun; Geng-Geng Luo; Na Zhang; Qin-Juan Xu; Cheng-Feng Yang; Zhan-Hua Wei; Yi-Chang Jin; Li-Rong Lin; Rong-Bin Huang; Lan-Sun Zheng (290-293).
The unprecedented μ3- and μ4-bonding modes of NH2pyz (NH2pyz = 2-aminopyrazine) are observed for the first time in a novel 3D Ag(I) coordination polymer [Ag7(NHpyz)6(ClO4)] n (1) which was obtained by reaction of Ag2O, NH2pyz and NaClO4 in H2O/CH3OH/NH3 media under ultrasonic treatment. Compound 1 is a 3D framework with infinite 1D Ag belts incorporating diverse Ag···Ag interactions. Moreover, 1 exhibits photoluminescence maximized at 494 nm upon 300 nm excitation at room temperature, which may be mainly assigned to ligand-to-metal charge transfer (LMCT) mixed with metal-centered (d-s/d-p) transitions. Semiconducting behavior of 1 was also measured at room temperature with σ value of 6.78 × 10−6  S cm−1.The unprecedented μ3- and μ4-bonding modes of NH2pyz (NH2pyz = 2-aminopyrazine) are observed for the first time in a novel 3D Ag(I) coordination polymer [Ag7(NHpyz)6(ClO4)] n (1) which was obtained by reaction of Ag2O, NH2pyz and NaClO4 in H2O/CH3OH/NH3 media under ultrasonic treatment. Compound 1 is a 3D framework with infinite 1D Ag belts incorporating diverse Ag···Ag interactions. Moreover, 1 exhibits photoluminescence maximized at 494 nm upon 300 nm excitation at room temperature, which may be mainly assigned to ligand-to-metal charge transfer (LMCT) mixed with metal-centered (d-s/d-p) transitions. Semiconducting behavior of 1 was also measured at room temperature with σ value of 6.78 × 10−6  S cm−1.
Keywords: Silver(I); 2-Aminopyrazine; Coordination polymer; Ag···Ag interaction; Photoluminescence;

A switch chemosensor for selective detection of Hg2+ can work via the conformation change of ferrocene by incorporating two well-known rhodamine-6G dyes and a ferrocene group within one molecule.A conformation flexible chemosensor for selective detection of Hg2+ in aqueous media was achieved by incorporating two well-known rhodamine-6G dyes and a ferrocene group within one molecule. Distinguished from the monosubstituted ferrocene derivative which is previously reported a lack of interaction with Hg2+, the title compound was characteristic of two-armed bidendate binding unit. The Hg2+ sensing behavior can be switched via the conformation flexibility. The 1:1 sensor/Hg2+ binding mode was proposed and supported by the titration experiment and ESI mass spectrum. The fluorescent sensor can display a highly selective response of fluorescence enhancement toward Hg2+ and detect the parts per billion (ppb) level of Hg2+ in aqueous environment.
Keywords: Chemosensor; Mercury; Fluorescence; Selectivity; Sensitivity;

A bimetallic oxide framework, [{Cu(bpy)}2Mo4O10(O3PCH2C6H4CH2PO3)2], constructed from novel { Mo 4 O 10 ( O 3 PR ) 4 } n 4 n - chains by Stephanie Jones; Hongxue Liu; Katherine Schmidtke; Charles C. O’Connor; Jon Zubieta (298-301).
The hydrothermal methods were used to prepare the bimetallic oxide phase [{Cu(bpy)}2Mo4O10(O3PCH2C6H4CH2PO3)2] (1). The three-dimensional structure of 1 is constructed from { Mo 4 O 10 ( O 3 PR ) 4 } n 4 n - chains, decorated with {Cu(bpy)}2+ subunits and linked through the p-xylyl tether of the diphosphonate ligand. Each phosphomolybdate chain is linked to four adjacent chains to generate the three-dimensional connectivity. As shown in the accompanying figure.The hydrothermal reaction of Cu(CH3CO2)2·H2O, MoO3, 2,2′-bipyridine (bpy), and p-xylene diphosphonic acid in the presence of HF provided blue crystals of the bimetallic oxide phase [{Cu(bpy)}2Mo4O10(O3PCH2C6H4CH2PO3)2] (1). The three-dimensional structure of 1 is constructed from { Mo 4 O 10 ( O 3 PR ) 4 } n 4 n - chains, decorated with {Cu(bpy)}2+ subunits and linked through the p-xylyl tether of the diphosphonate ligand. The molybdate building block within the chain is a tetranuclear {Mo4O10(O3P)8} cluster of edge- and corner-sharing {MoO6} octahedra. Each phosphomolybdate chain is linked to four adjacent chains to generate the three-dimensional connectivity. Crystal data: C18H16CuMo2N2O11P2, fw  = 753.69: monoclinic P21/c, a  = 7.9719(8) Å, b  = 14.0392(14) Å, c  = 21.274(2) Å, β  = 94.585(3)°, V  = 2373.3(4) Å3, Z  = 4, D calc  = 2.109 g cm−3, R 1  = 0.0610.
Keywords: Bimetallic oxide; Copper–molybdophosphonate material; Organic–inorganic hybrid material; X-ray structure;

A new hybrid compound, originated from Keggin-type polyoxoanions and hexanuclear metal–organic coordination complex macrocations, are reported, which represent the first example of host–guest compounds with double-Keggin anions as coordinating template.A new double-Keggin-anion-templated host–guest hybrid compound, (H4pzdc)5[(H2pzdc)6(pzdc)2(H2O)2Na6][PW12O40]4·31H2O (1) (H2pzdc = 2,3-pyrazinedicarboxylic acid), has been synthesized and characterized by elemental analysis, IR spectroscopy, TG analysis, and single crystal X-ray diffraction. Compound 1 exhibits an intriguing double-Keggin-anion-templated 2D structure, made up of [PW12O40]3− Keggin-type polyoxoanions covalently linked with hexanuclear [Na6(H2pzdc)6(pzdc)2]2+ macrocations. To our best knowledge, it represents the first example of host–guest compounds with double-Keggin anions as coordinating template. Furthermore, compound 1 displays stronger photoluminescence properties than the H2pzdc ligand, due to the introduction of alkali metal cations.
Keywords: Host–guest compound; Double-Keggin-anion template; Alkali metal coordination complex; Photoluminescence property;

A lamella 2D silver(I) coordination polymer constructed from in situ generated 2-mercaptobenzoic acid by Di Sun; Geng-Geng Luo; Na Zhang; Qin-Juan Xu; Yi-Chang Jin; Zhan-Hua Wei; Cheng-Feng Yang; Li-Rong Lin; Rong-Bin Huang; Lan-Sun Zheng (306-309).
The reaction of Ag2O with 2,2′-dithiodibenzoic acid (dtba) under ultrasonic condition gave rise to a novel coordination polymer [Ag4(2-mba)2·(H2O)2] n (1) (2-H2mba = 2-mercaptobenzoic acid) involving in situ generated 2-mba. Complex 1 shows a lamella 2D structure with a 63 -hcb net. Moreover, 1 exhibits photoluminescence and semiconductor properties.The reaction of Ag2O and 2,2′-dithiodibenzoic acid (dtba) under ultrasonic condition gave rise to a novel metal–organic coordination polymer [Ag4(2-mba)2·(H2O)2] n (1) (2-H2mba = 2-mercaptobenzoic acid) involving in situ generated 2-mba ligand. Complex 1 shows a lamella 2D structure with a 63 -hcb net which is comprised of fused Ag6 hexagonal rings. Moreover, 1 exhibits photoluminescence maximized at 468 nm upon 330 nm excitation at room temperature, which may be assigned to a ligand-to-metal charge transfer (LMCT) transition. Semiconducting behavior was also measured at room temperature with σ value of 3.24 × 10−5  S cm−1.
Keywords: Silver; 2,2′-Dithiodibenzoic acid; 2-Mercaptobenzoic acid; Metal–organic polymer; Photoluminescence; Semiconductivity;

The ligand-structure-selective binding of oligonucleotide by cobalt complexes by Huili Chen; Wei Gao; Fengmin Zhang; Chunjiao Dou; Pin Yang (310-313).
The ligand-structure-selective binding of oligonucleotide by cobalt complexes was proved by 2D NMR.The binding of two Co(III) complexes [Co(phen)2(DPQ)]3+ and [Co(phen)2(HPIP)]Cl3 [HPIP = 2-(2-hydroxyphenyl) imidazo [4,5-f][1,10] phenanthroline, DPQ = dipyrido[3,2-f:2′,3′-h]quinoxaline] to the normal base-paired decanucleotide d(CCTAATTAGG)2 was studied by 2D NMR. The results indicate that the width of intercalating ligand has a large effect on the selectivity of binding site. For [Co(phen)2(HPIP)]Cl3, the complex binds the decanucleotide at C2T3:G9A8 and A4A5:T7T6 by intercalation from the minor groove, while [Co(phen)2(DPQ)]3+ intercalates into T3A4:T7A8 region from the minor groove. The conclusion was further proved by molecular modeling.
Keywords: Oligonucleotide DNA; Cobalt complex; Intercalation; NMR;

DNA cleavage activities and mechanism of a novel heterodinuclear macrocyclic complex by Yuan He; Xiaohui Wang; Hong Zhou; Zhiquan Pan; Junbo Li; Qimao Huang (314-318).
A new unsymmetrical bis-furan pendant-armed macrocyclic heterodinuclear Cu(II)Zn(II) complex [CuZn(L)(OAc)](ClO4)·3CH3CN·H2O was synthesized and characterized. The viscosity, DNA binding and cleavage were also investigated.A new unsymmetrical bis-furan pendant-armed macrocyclic heterodinuclear Cu(II)Zn(II) complex, [CuZnL(OAc)](ClO4)·3MeCN·H2O(1) (H2L was derived from the condensation between 1,6-bis(2-furyl)-2,5-bis(2-hydroxy-3-formyl-5-bromobenzyl)-2, 5-diazahexane and 1,3-diaminopropane), has been synthesized and characterized by EDS (energy dispersive spectroscopy) and X-ray crystallography determination. The interaction between the complex and calf thymus (CT) DNA was investigated by UV–vis absorption, viscosity experiment, fluorescent and CD spectroscopy. The mechanism of the cleavage of supercoiled DNA (pBR 322DNA) process was also studied. It is proposed that DNA cleavage promoted by the complex occurrence via oxidative mechanism.
Keywords: Heterodinuclear complex; Binding-constants; Viscosity; DNA cleavage;

A new dinuclear cobalt compound, namely Co2(L)(H2O)Cl2 (1, H2L =  N,N′-o-phenylenebis(salicylide-neimine) was obtained by one-pot solvothermal self-assembly of CoCl2, 1,2-phenylenediamine, and salicylaldehyde in C2H5OH. The magnetic studies suggest weak antiferromagnetic behavior and the magnetic data were interpreted by means of a dinuclear cobalt model with the parameters of g  = 2.12, J  = −1.25 cm−1, θ  = −3.12 K.A new dinuclear cobalt compound, namely Co2(L)(H2O)Cl2 (1, H2L =  N,N′-o-phenylenebis(salicylide-neimine) was obtained by one-pot solvothermal self-assembly of CoCl2, 1,2-phenylenediamine, and salicylaldehyde in C2H5OH. The magnetic studies suggest weak antiferromagnetic behavior and the magnetic data were interpreted by means of a dinuclear cobalt model with the parameters of g  = 2.12, J  = −1.25 cm−1, θ  = −3.12 K.
Keywords: Solvothermal synthesis; Schiff base; Dinuclear cobalt compound; Antiferromagnetic interaction;

Three new coordination polymers based on 4-oxo-1(4H)quinolineacetate: Synthesis, structures and luminescent properties by Jun Wang; Jun Fan; Liang-Yu Guo; Xia Yin; Zhi-Hong Wang; Wei-Guang Zhang (322-325).
Reactions of Hoqa and varied metal salts resulted in the formation of three new coordination polymers, which exhibit two structure features, such as a 3D diamondoid network and 1D chain.Reactions of 4-oxo-1(4H)-quinolineacetic acid (Hoqa) and varied metal salts of Zn(II), Cd(II) and Ag(I) resulted in the formation of three new coordination polymers, namely, [Zn(oqa)2]·H2O (1), [Cd(bpy)(oqa)2(H2O)2]·4H2O (2) and [Ag(bpy)(oqa)]·2H2O (3) (bpy = 4,4′-bipyridine). Complex 1 has a three-dimensional (3D) polymeric network with diamondoid topology; compounds 23 exhibit one-dimensional (1D) chain structure characteristics, which are further assembled through π–π stacking attractions and hydrogen bonds, forming the 3D supramolecular frameworks. In addition, the solid-state luminescent properties of the ligand Hoqa and complexes 12 have been investigated at room temperature.
Keywords: 4-Oxo-1(4H)-quinolineacetate; Coordination polymers; Synthesis; Crystal structure; Luminescence;

Crystal structures and photoluminescence of the Zn(II) and Cd(II) complexes of N-methylpyrazinium obtained by a less hazardous approach by Chen Yang; Ming-Sheng Wang; Zhong-Ning Xu; Feng Chen; Guang-Ning Liu; Gang Xu; Guo-Cong Guo; Jin-Shun Huang (326-329).
A less hazardous approach has been used to synthesize N-methylpyrazinium cation ligand (mpz+). Three novel mpz+-containing complexes with interesting structural modes have been successfully obtained. Photoluminescent analyses reveal that three complexes exhibit strong blue emissions originating from intra-ligand π–π transition of the ligand.Compared to previously reported methods, a less hazardous approach has been used to synthesize N-methylpyrazinium cation (mpz+) by the reaction of pyrazine and ClCH2COONa. Although a few mpz+-containing complexes have been documented, there is no example of mpz+-containing group IIB metal complexes. Three novel complexes containing mpz+, (mpz)ZnI3 (1), [(mpz)CdCl3] n (2), and [(mpz)CdBr3] n (3), have been successfully obtained via a solution or hydrothermal method by reactions of ZnI2, CdCl2·2.5H2O, and CdBr2·4H2O with the mpz+ ligand, respectively. Complex 1 features an isolated structure, with each zinc atom coordinated by one mpz+ ligand and three terminal iodine atoms. The CD spectra of 1 reveal that it exhibits spontaneous resolution. Complexes 2 and 3 are isotypic, and exhibit chain structures made by linear arrays of Cd(II) bridged by halogen atoms. Photoluminescent analyses reveal that complexes 13 exhibit strong blue emissions originating from intra-ligand π–π transition of the mpz+ ligand.
Keywords: Cationic ligand; Group IIB metal complex; N-methylpyrazinium; Photoluminescence; Spontaneous resolution;