Inorganic Chemistry Communications (v.27, #C)

Contents List (iii-xiii).

Two ligand-bridged bicobaloximes, formed by replacement of pyridine (py) in monocobaloximes, [MeCo(dmgH)2(py)] (Me = methyl, dmgH = dimethylglyoxime) and MeCo(dpgH)2(py) (dpgH = diphenylglyoxime), by 4,4′-bipyridine and 2,4-di(1H-imidazol-1-yl)-6-methoxy-1,3,5-triazine, respectively, are reported. The crystal structures of the ligand-bridged bicobaloximes so obtained are described.The synthesis, structure and characterization of two ligand-bridged bicobaloximes, formed by replacement of pyridine (py) in monocobaloximes, [MeCo(dmgH)2(py)] (Me = methyl, dmgH = dimethylglyoxime) and MeCo(dpgH)2(py) (dpgH = diphenylglyoxime), by 4,4′-bipyridine and 2,4-di(1H-imidazol-1-yl)-6-methoxy-1,3,5-triazine, respectively, are reported.Display Omitted► Synthesis of two ligand-bridged bicobaloximes. ► Ligand displacement by other bulky organic ligands. ► The molecules are fitted through a locking system via C―H⋯π interactions in packing diagrams.
Keywords: Ligand-bridged bicobaloximes; NMR studies; Single X-ray crystal structures; Packing structure;

Reaction of 2,6-diacetylpyridine bis(4N-o-tolylthiosemicarbazone), H 2 L 1 , with K2PtCl4 and further recrystallization in DMSO/MeOH of the [PtL 1 ] complex obtained, led to the isolation of the novel platinum complex, [PtL 2 ], which was structurally characterized by single crystal X-ray diffraction. The molecular structure shows that the ligand has undergone an unexpected chemical transformation viz. reduction of one of the terminal phenyl rings into cyclohexyl. The resulted asymmetrical ligand acts a dianionic tetradentate donor, coordinating to the platinum(II) center in a square planar geometry through the Npyridinic atom and the Niminic and the S atoms from one thiosemicarbazone arm, the fourth coordination position is occupied by the Nhydrazinic atom of the other arm.A new neutral platinum(II) complex derived of 2,6-diacetylpyridine bis(thiosemicarbazone) ligand has been synthesized and structurally characterized by single crystal X-ray diffraction. The molecular structure shows that the ligand has undergone an unexpected chemical transformation via hydrogen transfer.Display Omitted► Evolution from α-N-heterocyclic bis(thiosemicarbazone) to a new asymmetric ligand. ► The Pt(II) complexes synthesized present uncommon thiosemicarbazone coordination. ► Molecular structure of the complex was confirmed by X-ray crystallography.
Keywords: Asymmetric N3S coordination; Bis(thiosemicarbazone); 2,6-diacetylpyridine; Platinum(II) complexes; Thiol function; X-ray diffraction;

Influences of oxide chemical modified on microstructure and electrical properties of PbTiO3-Bi(Ni1/2Ti1/2)O3 by Huajun Kang; Jun Chen; Laijun Liu; Changzheng Hu; Liang Fang; Xianran Xing (9-12).
The piezoelectric ceramics 0.45PbTiO3-0.55Bi(Ni1/2Ti1/2)O3 doped with PbO, Bi2O3, NiO and TiO2 were synthesized by conventional solid state reaction method. Thereafter, the structural, ferroelectric and piezoelectric properties of modified ceramics were investigated systematically. By adding Bi2O3, NiO and TiO2, the leakage current of ceramics was found to diminish pronouncedly. Moreover, the coercive field was observed to decrease by modification with TiO2 in these ceramics. It was also proven that NiO can only be added in the B-site in PT-55BNT from the results of X-ray photoelectron spectroscopy analysis. Therefore, the modification with oxides can inhibit the volatilization of Pb during the sintering process that eventually improves the performance of materials.By adding Bi2O3, NiO, and TiO2 the leakage current of ceramics can pronouncedly diminish. The modification of TiO2 can also reduce the coercive field. The X-ray photoelectron spectroscopy analysis measurements prove that NiO can only be added in B-site in PT-55BNT.Display Omitted► We do not introduce any other impurities. ► By adding Bi2O3, NiO, and TiO2 the leakage current of ceramics can obviously diminish. ► The XPS analysis tests prove that NiO can only be added in B-site in PT-55BNT.
Keywords: Chemical modification; Piezoelectrics; Ferroelectrics; PbTiO3-Bi(Ni1/2Ti1/2)O3;

An organic–inorganic hybrid 1-D double-chain copper–yttrium heterometallic silicotungstate [Cu(dap)2(H2O)]2{Cu(dap)2[α-H2SiW11O39Y(H2O)2]2}·10H2O by Jie Luo; Junwei Zhao; Jing Yuan; Yanzhou Li; Lijuan Chen; Pengtao Ma; Jingping Wang; Jingyang Niu (13-17).
An organic–inorganic hybrid 1-D double-chain CuII–YIII heterometallic silicotungstate [Cu(dap)2(H2O)]2 {Cu(dap)2[α-H2SiW11O39Y(H2O)2]2}·10H2O (1) has been synthesized by reaction of Na10[A-α-SiW9O34]·18H2O, CuCl2·2H2O, YCl3 and dap (dap = 1,2-diaminopropane) under hydrothermal conditions and characterized by elemental analyses, IR spectrum, UV spectrum and single-crystal X-ray diffraction. 1 exhibits a novel 1-D double-chain structure constructed from dimeric CuII–YIII heterometallic silicotungstate units. To our knowledge, 1 is the first organic–inorganic hybrid 1-D double-chain CuII–YIII heterometallic polyoxometalate. Thermogravimetry-differential thermal analysis of 1 has been measured from 25 to 750 °C and the thermogravimetric curve indicates two steps of weight loss.A 1-D double-chain CuII–YIII heterometallic silicotungstate [Cu(dap)2(H2O)]2{Cu(dap)2[α-H2SiW11O39Y(H2O)2]2}·10H2O has been synthesized and is the first organic–inorganic hybrid 1-D double-chain CuII–YIII heterometallic polyoxometalate.Display Omitted► copper–yttrium heterometallic silicotungstate ► 1-D double-chain structure ► hybrid 1-D double-chain CuII–YIII heterometallic polyoxometalate ► POM-based TM–RE heterometallic derivatives
Keywords: Polyoxometalate; Silicotungstate; Copper–yttrium heterometal; 1-D double-chain structure;

A novel Zn(II) metal-organic framework [Zn3(tib)2(L)3] (1) was synthesized with mixed ligands of 1,3,5-tris(1-imidazolyl)benzene (tib) and 4-carboxycinnamate (L2 −), exhibiting interesting two-fold interpenetration, where triple-stranded homochiral left- (L-) and right- (R-) handed helical chains were constructed by linear rigid ligand L2 − and metal ions. The complex was well characterized by single crystal and powder X-ray diffractions (PXRD), infrared spectroscopy (IR), elemental analysis (EA) and thermogravimetric analysis (TGA). As a result, the complex shows high thermal stability and strong photoluminescent emission in the solid state at room temperature.A novel Zn(II) complex [Zn3(tib)2(L)3] with mixed ligands of 1,3,5-tris(1-imidazolyl)benzene (tib) and 4-carboxycinnamate (L2 −), exhibiting interesting two-fold interpenetration of triple-stranded left- (L-) and right- (R-) handed helical chain based 3D nets was constructed and characterized.Display Omitted► Two-fold interpenetration of triple-stranded helical chain based 3D nets. ► Mixed ligands of 1,3,5-tris(1-imidazolyl)benzene and 4-carboxycinnamate. ► Fluorescence property.
Keywords: Zinc(II) metal-organic framework; Triple-stranded helical chains; Interpenetrating; High thermal stability; Photoluminescence;

Construction of one pH-independent 3-D pillar-layer lead-organic framework containing tetrazole-1-acetic acid by Ling Chen; Hong-Yang Jia; Xu-Jia Hong; Dan-Hua Chen; Zhi-Peng Zheng; Hong-Guang Jin; Zhi-Gang Gu; Yue-Peng Cai (22-25).
One new 3-D PbII complex, {[Pb2(tza)(μ 3-OH)(μ 3-Cl)(μ 4-Cl)]n (1) (Htza = tetrazole-1-acetic acid), has been synthesized from the reaction of tetrazole-1-acetic acid (Htza) with PbCl2 at pH = 8.5 under hydro-solvent condition and characterized by X-ray single crystal diffraction, elemental analysis, thermogravimetric analysis, and IR spectra. The results show that the coordination chemistry of the multi-dentate ligand Htza on PbII ion has good pH sensitivity. At pH = 5 and 7, two once reported 3-D framework complexes {[Pb(tza)2]n (2) and [Pb(tza)(μ 3-Cl)]n (3) are obtained, respectively. And then at pH = 8.5, the resultant three-dimensional complex 1 presents the pillar-layer framework network with a thickness of 8.25 Å of layer [Pb2(μ 3-OH)(μ 2-O)2(μ 3-Cl)(μ 4-Cl)]n, in which there still exists the μ 3-bridging mode of OH group and the μ 2-carboxyl oxygen atom besides the μ 3- and μ 4-bridging manners of the Cl ion. Furthermore, the luminescent property of complex 1 has also been investigated, and the result exhibits blue photoluminescence in the solid state at room temperature, which shows that this complex may be a good candidate for photoactive material.One new 3-D pH-independent lead-organic framework constructed from two-dimensional oxo-/Cl-bridged lead-based layers {[Pb4(μ 3-OH)2(μ 2-O)2(μ 3-Cl)2(μ 4-Cl)2}n and tza pillars was synthesized and characterized. The blue fluorescence property in the solid state at room temperature shows the title complexes may be good candidates for photoactive material.Display Omitted► One 3D framework from [Pb4(μ 3-OH)2(μ 2-O)2(μ 3-Cl)2(μ 4-Cl)2]n layer and tza pillar ► 2-D lead-based layer is formed via oxo-/Cl-bridges. ► The complex is one good candidate for photoactive material.
Keywords: pH-independence; 3-D pillar-layer framework; Lead complex; Tetrazole-1-acetic acid; Photoluminescence;

New molybdenum(VI) complex with ONS-donor thiosemicarbazone ligand: Preparation, structural characterization, and catalytic applications in olefin epoxidation by Zeinab Moradi-Shoeili; Davar M. Boghaei; Mojtaba Amini; Mojtaba Bagherzadeh; Behrouz Notash (26-30).
New dioxomolybdenum(VI) complex was prepared by reacting 1-(2,4-dihydroxybenzylidene)-N-methyl-N-phenylthiosemicarbazone (H2L) as ligand and [MoO2(acac)2] in acetonitrile solution. The doubly deprotonated ligand is coordinated to molybdenum through sulfur atom, hydrazinic nitrogen atom and phenolic oxygen atom. The resulting complex with the formula [MoO2L(CH3CN)] which contains an acetonitrile molecule in sixth site of coordination, was characterized by elemental analyses, 1H NMR, IR and electronic spectroscopic studies and single crystal X-ray diffraction analysis. This complex was tested as a catalyst for the homogeneous epoxidation of olefins using tert-butyl hydrogen peroxide (TBHP) as an oxidant. The catalyst shows efficient reactivity in the olefins epoxidation reactions giving high yield and selectivity under atmospheric conditions, in most cases.New dioxomolybdenum(VI) complex with the formula [MoO2L(CH3CN)] which contains an acetonitrile molecule in sixth site of coordination, was prepared and structurally characterized. The complex shows efficient catalytic reactivity in the olefins epoxidation reactions using tert-butyl hydrogen peroxide (TBHP) as an oxidant.Display Omitted► New mononuclear dioxomolybdenum(VI) complex was prepared and characterized. ► The MoO2 2 + moiety is coordinated to ONS-donor ligand and acetonitrile molecule. ► The complex shows efficient catalytic reactivity in the olefins epoxidation.
Keywords: Dioxomolybdenum(VI) complex; Thiosemicarbazone; Olefin epoxidation;

A novel nitronyl nitroxide radical and its Gd(III), Tb(III), Dy(III) complexes: Synthesis, structure and magnetic properties by Yuan-yuan Gao; Ya-li Wang; Peng Hu; Ming-fang Yang; Yue Ma; Qing-lun Wang; Li-cun Li; Dai-zheng Liao (31-35).
Three new lanthanide complexes based on a novel nitronyl nitroxide radical [Ln(hfac)3(NITPhiPr)2] (Ln = Gd(1), Tb(2), Dy(3); hfac = hexafluoroacetylacetonate, NITPhiPr = 4′-isopropyl-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) have been successfully synthesized, characterized structurally and magnetically, which all display radical-Ln(III)-radical tri-spin structures. The magnetic studies reveal the ferromagnetic interactions between the Gd(III) ion and radicals and the antiferromagnetic interaction between two radicals in the complex 1. And both Ln(III)–radical ferromagnetic interactions exist in complexes 2 and 3.A novel radical and its three mononuclear Gd (III), Tb (III), Dy (III) tri-spin complexes were successfully synthesized and characterized magnetically. The magnetic studies reveal that all lanthanide–radical ferromagnetic interactions exist in complexes 13.Display Omitted► Three lanthanide–radical complexes were successfully synthesized. ► All ferromagnetic interactions exist in complexes 1–3. ► Simplified model was carried out to evaluate the coupling in complex 1.
Keywords: Nitronyl nitroxide radical; Lanthanides; Crystal structure; Magnetic properties;

Simple synthesis and structure characterization of a phosphoniomethylidyne tantalum(V) complex by Nazhen Liu; Gengyu Zhu; Hongjian Sun; Xiaoyan Li (36-39).
A high-valent phosphoniomethylidyne tantalum complex [(C5Me4H)Ta(C-PPh3)(=CH-PPh3)Cl] (3) was obtained via transylidation reactions of (C5Me4H)TaCl4 with 5 equivalents of the phosphorus ylide Ph3P = CH2. The addition of strong base Li(N(SiMe3)2 is beneficial to the transylidation reaction and improves the yield of complex 3. The ylide adduct complex [(C5Me4H)TaCl4(CH2PPh3)] (4) as the reaction intermediate was isolated through the reaction of (C5Me4H)TaCl4 with one equivalent of the phosphorus ylide Ph3P = CH2. Both complexes 3 and 4 were structurally characterized by X-ray single crystal diffraction. A comparison on the preparation and properties of the phosphoniomethylidyne tantalum complexes with different supporting ligands, [CpTa(C-PPh3)(=CH-PPh3)Cl] (1) (Cp = cyclopentadieneyl ligand), [(C5Me4H)Ta(C-PPh3)(=CH-PPh3)Cl] (3) (C5Me4H = tetramethylcyclopentadienyl ligand) (3) and [CpTa(C-PPh3)(=CH-PPh3)Cl] (2) (Cp = pentamethylcyclopentadienyl ligand) was discussed.A high-valent tantalum(V) phosphoniomethylidyne complex [(C5Me4H)Ta(C-PPh3)(=CH-PPh3)Cl] (3) was obtained via transylidation reactions of (C5Me4H)TaCl4 with 5 equiv of the phosphorus ylide Ph3P = CH2. With the addition of 3 equiv of LiN(SiMe3)2 and 3 equiv of Ph3P = CH2 complex 3 could be quantitatively obtained within 12 h.Display Omitted► Synthesis and characterization of a tantalum(V) phosphoniomethylidyne complex. ► Transylidation reactions. ► Tantalum(V) ylide adduct complex. ► Tantalum(V) complex with tetramethylcyclopentadienyl ligand.
Keywords: Phosphoniomethylidyne complex; Tantalum; Tetramethylcyclopentadiene; Phosphorus ylide;

N-[N′,N′-Methylphenylamino(thiocarbonyl)]benzimidoyl chloride (1) reacts with in situ-prepared arylselenolates or aryltellurolates under formation of the first representatives of the corresponding iminoselenides or -tellurides. The products are air-stable solids, which have been studied spectroscopically and by single-crystal X-ray diffraction.N-[N′,N′-Methylphenylamino(thiocarbonyl)]benzimidoyl chloride (1) reacts with in situ-prepared arylselenolates or aryltellurolates under formation of the first representatives of the corresponding iminoselenides or -tellurides.Display Omitted► Iminoselenides are formed from benzimidoyl chlorides and arylselenolates. ► Analogous tellurium compounds are accessible from aryltellurolates. ► The products are stable as solids and in solution. ► Monomeric or pseudo-dimeric solid state structures have been found.
Keywords: Tellurium; Selenium; Thiourea derivatives; X-ray structure;

A novel 2D organic–inorganic hybrid based on [P2W18O62]6− polyoxoanion and Cu–bbi coordination polymers by Heng Guo; Kai Yu; Zhanhua Su; Chunmei Wang; Chunxiao Wang; Baibin Zhou (43-46).
A novel 2D compound based on Wells–Dawson polyoxometalates, [Cu3(bbi)6(P2W18O62)] (bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) (1) has been hydrothermally synthesized and characterized by elemental analyse, IR, TG, PXRD and single crystal X-ray diffraction. In compound 1, each Cu2+ ion is connected with four adjacent Cu2+ ions by bbi ligands along four different directions and each bbi ligand is two-coordinated by two Cu2+ ions, which results in an unusual 2D interlink lock-liked layer. Interestingly, two kinds of macrocycles exist in the structure, in which six smaller 33-membered rings are placed end to end to form the larger ones (66-membered macrocycles). The [P2W18O62]6− polyoxoanions as bidentate ‘guest’ is incorporated into the larger macrocycles. These 2D layers are further packed into 3D framework through strong supramolecular interactions. Additionally, electrochemical and electrocatalysis behavior of 1-CPE have been studied in detail.A 2D hybrid based on Wells–Dawson, [Cu3(bbi)6(P2W18O62)] (bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) (1) is reported. The compound 1 is the first example of framework constructed by interlink lock-liked Cu–bbi complex layer and bidentate guest units [P2W18O62]6− polyoxoanions. Two kinds of macrocycles exist in the layer. Electrochemical analysis shows that 1-CPE displays unique redox properties and good electrocatalytic activity to reduce H2O2.Display Omitted► Copper (II) ions and bbi ligands form a 2D interlink lock-liked layer. ► Two kinds of macrocycles exist in the layer. ► The [P2W18O62]6– anion as bidentate ‘guest’ is embedded into the larger macrocycles. ► 1-CPE displays unique redox properties and electrocatalytic activity to H2O2.
Keywords: Hydrothermal synthesis; Flexible ligands; Wells–Dawson polyoxometalates; Electrochemical property;

We report the crystal structure and magnetic properties of a two-dimensional cyano-bridged MnII(S  = 5/2)–NbIV(S  = 1/2) bimetal assembly (1), and the magnetic properties of an isostructural cyano-bridged MnII–MoIV(S  = 0) bimetal assembly (2). 1 contains 3-hydroxypyridine ligands with four types of coordination arrangements, includes μ-oxo-bridged Mn–Mn sites, and shows ferrimagnetism with a Curie temperature of 16 K due to the antiferromagnetic MnII–NbIV superexchange interaction through the cyano groups. 2 exhibits paramagnetism with the antiferromagnetic interaction between Mn and Mn through the μ-oxo-bridges.2-D cyano-bridged MnII-NbIV bimetal assembly includes four different coordination arrangements of 3-hydroxypyridines and μ-oxo-bridged Mn-Mn sites, exhibiting ferrimagnetism with T C of 16 K due to the antiferromagnetic interaction of Nb―C≡N―Mn. The isostructural MnII-NoIV assembly shows paramagnetism.Display Omitted► 2-D cyano-bridged MnII(S  = 5/2) –NbIV(S  = 1/2) bimetal assembly 1 and isostructural MnII–MoIV(S  = 0) compound 2 are prepared. ► Compound 1 includes four different coordination arrangements of 3-hydroxypyridines. ► Compound 1 contains μ-oxo-bridged Mn–Mn sites in the cyano-bridged network. ► Compound 1 exhibits ferrimagnetism with T C of 16 K due to the antiferromagnetic superexchange interaction of Nb―C ≡ N―Mn. ► Compound 2 shows paramagnetism due to the antiferromagnetic superexchange interaction of Mn–Mn through μ-oxo-bridges.
Keywords: Cyano-bridged bimetal assembly; Octacyanoniobate; Ferrimagnetism; Antiferromagnetic superexchange interaction; Niobium; Manganese;

The mixed ligand Cu(II) complexes of ciprofloxacin and N, O donor Schiff bases have been prepared and characterized by physicochemical techniques. In these complexes, ciprofloxacin acts as bidentate deprotonated ligand bound to the metal through the pyridone oxygen and one carboxylate oxygen. The antimicrobial activity of the complexes has been tested on three Gram(− ve) and two Gram(+ ve) microorganisms in terms of minimum inhibitory concentration (MIC) and colony forming unit (CFU). The interaction study of the complexes with Herring Sperm DNA (HS-DNA) has been performed by absorption titration and viscosity measurement. The DNA cleavage activity has been carried out by gel electrophoresis experiment using supercoiled form of pUC19 DNA. Potential cytotoxic effect of complexes has been investigated by brine shrimp lethality assay method. The complexes have been also screened for their enzymatic behaviour in terms of IC50 value.Square pyramidal copper(II) complexes have been synthesized using ciprofloxacin and N, O donor ligands. Their antibacterial, DNA interaction, cytotoxic and SOD like activity have also been evaluated.Display Omitted► Synthesis of substituted N, O donor ligands and their Cu(II) complexes. ► Complexes have been characterized of by physico-chemical techniques. ► The interaction of copper(II) complexes with DNA has been studied.
Keywords: Copper(II) complexes; MIC; DNA interaction; DNA cleavage activity; Cytotoxicity; Enzymatic behaviour;

Synthesis and photochemical properties of unsymmetrical phthalocyanine bearing two 1-adamantylsulfanyl groups at adjacent peripheral positions by Michal Kryjewski; Michal Nowak; Piotr Kasprzycki; Piotr Fita; Czeslaw Radzewicz; Tomasz Goslinski; Jadwiga Mielcarek (56-59).
A novel unsymmetrical magnesium(II) 2,3-bis(1-adamantylsulfanyl)phthalocyanine was prepared by mixed macrocyclization reaction of two phthalonitriles (phthalonitrile and 4,5-bis(1-adamantylsulfanyl)phthalonitrile) and characterized using UV–vis, MALDI MS and NMR methods. Precursor adamantyl disubstituted phthalonitrile was synthesized from 4,5-dichlorophthalonitrile. Absorption and emission properties of this novel phthalocyanine were investigated, including determination of fluorescence quantum yields, fluorescence lifetimes and solvatochromic effects. This newly synthesized phthalocyanine can be considered as a potential photosensitizer, as its singlet oxygen quantum yield (ΦΔ) of 0.49 was found in DMF and DMSO.New, unsymmetrical phthalocyanine bearing 1-adamantylsulfanyl moieties was synthesized, characterized and subjected to photochemical studies. The phthalocyanine was subjected to solvatochromic studies, and fluorescence quantum yields and fluorescence lifetimes were measured. Phthalocyanine was evaluated as potential photosensitizing agent by determining its ability to generate singlet oxygen.Display Omitted► Phthalocyanine with 1-adamantylsulfanyl moieties was synthesized and characterized. ► The fluorescence quantum yields and fluorescence lifetimes were measured. ► The singlet oxygen quantum yields were determined..
Keywords: Phthalocyanine; Adamantane; Singlet oxygen; Photosensitizer; Solvatochromic effects;

[PtCl2(dppe)] (dppe = 1,2-bis(diphenylphosphino)ethane) reacts with pyrazol-1-yl- (L1), 3,5-dimethylpyrazol-1-yl- (L2), and indazol-1-yl- (L3) dithiocarbamate to form [Pt(L1)2(dppe)] (1), [Pt(L2)2(dppe)] (2) and [Pt(L3)2(dppe)] (3). These complexes readily transform into [Pt(S2CO)(dppe)] (4) in chloroform and dichloromethane at room temperature. Stability of the bis(dithiocarbamate)platinum complex from L2, [Pt(L2)2] (5) suggests that the transformation of 13 to 4 is facilitated by the phosphine ancillary ligand.Bis(diphenylphosphino)platinum(II) chloride reacts with heterocycle-based dithiocarbamates as ligands to form platinum complexes, which in solution, readily transform the dithiocarbamate ligands into oxodithiocarbonate.Display Omitted
Keywords: Dithiocarbamate platinum; Bis(diphenylphosphino)ethane; Transformation of dithiocarbamate; Oxodithiocarbonate;

Magnetically-recoverable Pd-immobilized layered double hydroxide–iron oxide nanocomposite catalyst for carbon–carbon cross-coupling reactions by Ahmet N. Ay; Natalya V. Abramova; Deniz Konuk; Olga L. Lependina; Viacheslav I. Sokolov; Birgül Zümreoglu-Karan (64-68).
A novel magnetic composite catalyst has been prepared by immobilizing a palladium(0) complex, Pd2(dba)3, onto Mg–Al-layered double hydroxide shell supported on magnetite core. This new catalyst was characterized by XRD, TEM, EDX, FTIR, XPS, thermogravimetry and microanalytical techniques and magnetometric measurements. The performance of the catalyst was tested in the Heck and Suzuki reactions and confirmed to be efficient in the cross-coupling of aryl iodides under mild conditions.A novel catalytic system active in the Heck-Mizoroki and Suzuki-Miyaura reactions is reported. The system is prepared by incorporating Pd2(dba)3 to a Mg-Al-LDH shell supported on magnetite core. The magnetically recoverable catalyst exhibited moderate activity with aryl iodides in carbon-carbon cross-coupling reactions.Display Omitted► Pd2(dpa)3 was immobilized on Mg–Al–LDH shell supported on magnetite core. ► The magnetically recoverable nanocomposite catalyst displayed soft ferromagnetism. ► Pd-LDH@M moderately catalyzed cross-coupling reactions of aryl iodides.
Keywords: Palladium; Heck and Suzuki reactions; Layered double hydroxide; Core–shell; Magnetic catalyst; Heterogeneous catalyst;

Hydrothermal syntheses and crystal structures of PbII coordination polymers based on a N,O-donor ligand by Chun-Bo Liu; Shan-Shan Wang; Guang-Bo Che; Han Zhao; Wei-Wei Li; Xiu-Ying Li; Zhan-Lin Xu (69-75).
In this article, four new lead(II) coordination polymers based on a N,O-donor ligand 2′-(1 H-1,3,7,8-tetraaza-cyclopenta[l]phenanthren-2-yl)biphenyl-2-carboxylic acid (HL) have been hydrothermally synthesized, namely, [PbL2]·2H2O (1), [PbL2]·2H2O·CH3CH2OH (2), [Pb5L2(m-BDC)4]·3H2O (3) and [Pb2L2(p-BDC)] (4), where m-BDC = 1,3-benzenedicarboxylate and p-BDC = 1,4-benzenedicarboxylate. Compound 1 shows a 2D bilayer structure, which is further extended into a 3D supramolecular structure through π–π stacking interactions. Compound 2 shows a 3D supramolecular structure based on a zero-dimensional molecule by π–π stacking interactions of neighboring molecules. Compound 3 shows a 2D layer structure. Compound 4 displays a 1D chain-like structure, which is then stacked by π–π interactions to result in a 2D supramolecular structure. Solid-state luminescent spectra of four lead(II) complexes indicate intense fluorescent emissions.Four PbII metal-organic frameworks with distinct structures based on a N,O-donor ligand have been successfully synthesized by varying the solvents and organic aromatic acids, where photoluminescent properties were also investigated.Display Omitted► Four lead(II) complexes have been hydrothermally synthesized. ► Phenanthroline derivative and two aromatic acids were used as the ligands. ► PL spectra of four complexes indicate intense fluorescent emissions.
Keywords: Lead(II); N,O-donor ligand; Benzenedicarboxylate; Crystal structure;

A 3D chiral coordination polymer, [Co3(hfipbb)2(D-Hcam)2(bpp)2(H2O)2]·2H2O (1) (H2hfipbb = 2,2-bis(4-carboxyphenyl)hexafluoropropane, D-H2cam = D-(+)camphoric acid, bpp = 1,3-di(4-pyridyl)propane), has been hydrothermally synthesized, which features an interesting 6-connected self-interpenetrating (44.610.8) topological network. There exists predominantly antiferromagnetic interaction between the Co(II) centers in 1.A 3D chiral coordination polymer, [Co3(hfipbb)2(D-Hcam)2(bpp)2(H2O)2]·2H2O (1) (H2hfipbb = 2,2-Bis(4-carboxyphenyl)hexafluoropropane, D-H2cam = D-(+)camphoric acid, bpp = 1,3-di(4-pyridyl)propane), has been hydrothermally synthesized, which features an interesting 6-connected self-penetrated (44.610.8) topological network.Display Omitted► A 3D chiral Co(II) coordination polymer ► Features an interesting 6-connected self-penetrated (44.610.8) topological network ► There exists predominantly antiferromagnetic interaction between the Co(II) centers.
Keywords: Coordination polymer; Chirality; Hydrothermal synthesis; Crystal structure; Magnetism;

Synthesis, crystal structure and nonlinear optical property of CsV2O5 by Hong Luo; Jianguo Pan; Bingqian Lou; Yuebao Li; Xing Li; Lei Han (79-81).
The new nonlinear optical crystal CsV2O5 has been synthesized by solid state reaction and characterized by single-crystal X-ray diffraction and thermogravimetric analysis. The crystal CsV2O5 crystallizes in the orthorhombic system with space Ima2 space group. It is a layered structure that is very flat and strongly parallel to c. The striking structural feature is that the V atom in single crystallographic site has two different valence states (V4+ and V5+). The [V2O5]n layer consists of corner-linked tetrahedron. The six tetrahedrons lie very nearly in the same z-plane forming almost regular hexagons. The Kurtz powder SHG measurement, using 1064 nm radiation, showed that the second-harmonic generation efficiency of CsV2O5 is about six times that of KDP.View of the structure of CsV2O5, corner-connected VO4 triangular pyramids interspersed with layers Cs ions.Display Omitted► The nonlinear optical crystal CsV2O5 has been synthesized by solid state reaction. ► The complexes have been characterized by single crystal X-ray diffraction. ► The second-harmonic generation efficiency of CsV2O5 has been measured.
Keywords: Crystal structure; Nonlinear optical material; CsV2O5;

Polynuclear oxovanadium(IV) Schiff base complex [VOL2] n of bidentate NO Schiff base ligand (L = 5-bromo-2-hydroxybenzyl-2-furyl(methyl)imine) was synthesized and characterized by elemental analysis and FT-IR spectroscopy. The crystal structure of [VOL2] n has been determined by single crystal X-ray diffraction. The complex has two symmetry independent vanadium centers located on a two-fold axis. Both centers have a distorted octahedral N2O4 coordination sphere. Two Schiff base ligands act as chelating ligands and coordinate to the vanadium center each via one nitrogen and one oxygen atom. The remaining two apices of the octahedron are occupied by oxygen shared by the neighboring vanadium atoms, giving rise to 1D coordination polymer [VOL2] n with the interatomic V···V distance 3.7670(6) Å. This complex is used as a catalyst for the epoxidation of the cyclooctene. Different reaction parameters were optimized and the results showed that it can be active and selective in the optimized conditions. After thermal decomposition of the complex, the XRD pattern of the obtained solid shows the formation of the V2O5 nano particles with the average size of 41 nm.The new polynuclear [VIVOL2]n Schiff base complex, was prepared, characterized by FT-IR spectrum, CHN and single crystal X-ray analysis and used as a homogeneous catalyst in the epoxidation of cyclooctene. The results showed that it was highly active and selective catalyst in optimized conditions in epoxidation of cyclooctene.Display Omitted► A new polynuclear oxovanadium(IV) Schiff base complex, [VIVOL2] n was prepared. ► It crystallizes in the monoclinic space group C2/c. ► Its catalytic activity was tested in the epoxidation of the cyclooctene. ► The results showed that it was highly active and selective catalyst. ► Thermal decomposition of [VIVOL2] n resulted in formation of the V2O5 nano-particles.
Keywords: Polynuclear oxovanadium(IV); Schiff base; Crystal structure; Epoxidation;

Flexible carboxylic ligands have attracted considerable interest due to their excellent stretchable capacity and coordinative ability. In this paper, one new 2D zinc coordination polymer {[Zn(tcpob)2/3(H2O)2/3]·(H2O)2/3}n with trinuclear zinc cluster units was prepared under hydrothermal conditions based on 1,3,5-tri(4-carboxyphenoxy)benzene ligand. In addition, the solid-state photoluminescent spectra were measured at room temperature.Self-assembly of a triangle flexible carboxylic acid and Zn salt under solvothermal conditions generated a new 2D coordination polymer with trinuclear zinc cluster units.Display Omitted► Triangle flexible carboxylic ligand acts as the bridging ligand. ► Characterization by elemental analysis, IR, PXRD and X-ray crystallography. ► AB stacking structure including trinuclear zinc cluster units. ► Emission of the complex is attributed to charge transfer of internal ligand.
Keywords: Trinuclear core; Flexible carboxylic ligand; Coordination polymer;

[Ni(dien)2]3[Ge3Sb8S21]·0.5H2O: A new 2-D layered thiogermanate–thioantimonate with metal complexes as template ions by Jian Zhou; Xing Liu; Guoming Liang; Weijiang Liang; Feilong Hu; Ligang Zhu (92-96).
A new 2-D layered thiogermanate–thioantimonate [Ni(dien)2]3[Ge3Sb8S21]·0.5H2O (1, dien = diethylenetriamine) was synthesized under solvothermal conditions and structurally characterized. The polymeric [Ge3Sb8S21]6n n anion in 1 is composed of heterometallic semicube [GeSb2S7] clusters and trigonal-pyramidal [SbS3] units, which are interconnected to build a 2-D layer with the large Sb18S18 heterorings. The apertures of the Sb18S18 heterorings are filled by three [Ni(dien)2]2+ complex cations as template ions. The absorption band edge of 1 is 2.29 eV, exhibiting properties of the semiconductor.The linkage of heterometallic semicube [GeSb2S7] clusters and trigonal-pyramidal [SbS3] units into a 2-D sheet layer with the larger Sb18S18 heterorings, which are filled by [Ni (dien)2]2+ complex cations.Display Omitted► One new thiogermanate–thioantimonate was obtained under solvothermal conditions. ► Metal complexes of compound 1 reside within the cavities of the 2-D Ge―S―Sb layer. ► Compound 1 exhibits properties of the semiconductor.
Keywords: Solvothermal synthesis; Thiogermanate; Thioantimonate; Transition metal complex; Crystal structure;

A novel one-dimensional helical mixed-valence cobalt coordination polymer (1) {[CoIICoIII(HL)2(OAc)]·CH3OH·H2O}n, ( H 3 L  = 2-ethyl-2-((2-hydroxynaphthalen-1-yl)methyleneamino)propane-1,3-diol) has been synthesized and characterized. Single-crystal X-ray diffraction analyses reveal that complex 1 crystallizes in the tetragonal I4(1)/a space group. It consists of a bimetallic CoIICoIII2-O)2 core, and the adjacent CoII(2) centers are sequentially bridged by carboxylate groups in the syn–anti fashion, affording to a one-dimensional infinite helical chain along the c-axis. Adjacent chains are stacked via C―H···π interactions to form the overall three-dimensional supramolecular networks. Magnetic and in vitro anticancer activities of the complex have been investigated in detail.Susceptibility data for {[CoIICoIII(HL)2(OAc)]·CH3OH·H2O}n in χ M T (○) vs. T(Δ).Display Omitted► 1D mixed-valented cobalt coordination polymer are synthesized and characterized. ► Carboxylate groups bridge in the syn–anti fashion, leading to right-helice. ► Weak FM exchange interaction may occur in complex. ► In vitro anticancer activity of the complex are determined against A-549 cells.
Keywords: Mixed-valence cobalt complex; Carboxylate bridging; Coordination polymer; Magnetism; Anticancer activity;

Poly(propylene imine) (PPIs) dendrimers modified with glyceryl moieties: Powerful catalysts for catecholase by Karim Fhayli; Sylvain Gatard; Aminou Mohamadou; Laurent Dupont; Sandrine Bouquillon (101-104).
Poly(propylene imine) (PPIs) dendrimers modified with glyceryl moieties (GD-PPIs) have shown a dramatic positive effect in the aerial oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butyl-o-quinone (3,5-DTBQ), catalyzed by copper(II) acetate. These dendritic effects are of great interest for degradation reactions of phenolic micropollutants for environmental purposes.Display Omitted► PPI dendrimers functionalized with glyceryl moieties for complexing Cu(II). ► Catalyzing the oxidation of 3,5-DTBC as a model of phenolic micropollutants. ► A positive dendritic effect in the oxidation reaction of 3,5-DTBC.
Keywords: Dendrimers; PPI; Glycerol; Catecholase; Catalysis;

A non-interpenetrating eight-connected 3D coordination network consisting of dinuclear Ni(II) units by Xiaoju Li; Xiaofang Guo; Xiahong Xu; Guangchao Ma; Shen Lin (105-107).
An eight-connected 3D coordination polymer consisting of water-bridged dinuclear Ni(II) units has been prepared. The complex exhibits an unprecedented non-interpenetrating framework.An eight-connected 3D coordination polymer has been synthesized and characterized. The complex is non-interpenetrating and consists of the water-bridged dinuclear Ni(II) units.Display Omitted► A 3D coordination polymer consisting of dinuclear Ni(II) units was prepared. ► The complex is an eight-connected network. ► The framework of the complex is non-interpenetrating.
Keywords: Carboxylate; Coordination polymer; Crystal structure; Nickel(II);

Synthesis and characterization of ruthenium (II) carbonyl complexes containing naphthyridine and acetylacetonate ligands and their catalytic activity in the hydrogen transfer reaction by Sergio A. Moya; Juan Carlos Araya; Juana Gajardo; Véronique Guerchais; Hubert Le Bozec; Loïc Toupet; Pedro Aguirre (108-110).
A series of novel complexes of the Ru(L)2(CO)2 L = 2-(3′ methoxyphenyl)-1,8-naphthyridine (complex 1), and type Ru(acac)2(L)(CO) with L = 2-(3′ methoxyphenyl)-1,8-naphthyridine (complex 2), 2-(2′-bromophenyl)-1,8-naphthyridine (complex 3) and 2-phenyl-1,8-naphthyridine (complex 4) was synthesized and characterized. We found that the complexes 2, 3, and 4 can be directly synthesized from Ru3(CO)12. The complex Ru(acac)2(L)(CO) L = 2-(3′ methoxyphenyl)-1,8-naphthyridine (2) was characterized by X-ray single crystal analysis which confirms the monodentate coordination mode of the 1,8-naphthyridine derivate and the cis arrangement of the acac ligands. Preliminary studies in transfer hydrogenation of acetophenone in the presence of 2-propanol show the good catalytic activity of complex 2 with 92% conversion.A series of novel complexes of the Ru(L)2(CO)2 L = 2-(3′ methoxyphenyl)-1,8-naphthyridine (complex 1), and type Ru(acac)2(L)(CO) with L = 2-(3′ methoxyphenyl)-1,8-naphthyridine (complex 2), 2-(2′-bromophenyl)-1,8-naphthyridine (complex 3) and 2-phenyl-1,8-naphthyridine (complex 4) were synthesized and characterized.Display Omitted► Ruthenium naphthyridine complexes were successfully achieved in hydrogenation. ► Ruthenium naphthyridine carbonyl complexes were synthesized. ► One pot synthesis for the ruthenium complexes using a single procedure is reported. ► The crystal structure confirms the monodentate ruthenium naphthyridine complexes.
Keywords: Ruthenium(II); 1,8-Naphthyridine; Carbon monoxide; Acetylacetonate complexes; Transfer hydrogenation; Acetophenone;

A new 3D metal–organic framework [Cd2(2,6-pydc)2(bime)(H2O)]n (1) containing 1D Cd − oxygen chains was synthesized by the self-assembly of pyridine-2,6-dicarboxylate (2,6-pydc), 1,6-Bis (imidazol) hexane (bime) and Cd(II) salt, which exhibits a 2-fold interpenetrated 3D entanglement architecture with attractive helical structure. In addition, photoluminescent and thermal properties of complex 1 have been investigated as well.Under hydrothermal condition an interesting 3D 2-fold interpenetrated framework constitutes 1D cadmium − oxygen chains and shows left- and right-handed helical chain in one network.Display Omitted► A new 3D metal-organic framework containing 1D Cd−oxygen chains. ► A 2-fold interpenetrated entanglement architecture with helical structure. ► Photoluminescent property of 1 has been investigated.
Keywords: Metal–organic framework; Cadmium–oxygen chain; Luminescent property;

Six new complexes 16 with the common formula [M(NiL)4][M(NCS)4] (M = Mn, Fe, Co, Ni, Cu and Zn for 1, 2, 3, 4, 5 and 6, respectively; the same below) were synthesised and structurally characterised by X-ray single crystal analysis. NiL acts as a complex ligand. L denotes the dianion of dimethyl 5,6,7,8,15,16-hexahydro-6,7-dioxodibenzo-[1,4,8,11]tetraazacyclotetradecine-13,18-dicarboxylate. Each M(II) centre of the [M(NiL)4]2 + complex cations in 1–6 adopts a distorted square-antiprism coordination geometry with a O8 donor set. All the M―O bonds in the six complexes are abnormally long (2.444–2.528 Å). M(II) complexes having such weak coordination environments have not been reported, and eight-coordinate M(II) complexes with all the eight oxygen donor atoms coming from metalloligands have also not been documented. Each M(II) centre of the [M(NCS)4]2 − anions in 16 has a distorted tetrahedral coordination environment with a N4 donor set. Theoretical calculations for the bond dissociation energies (BDEs) of the M―O semi coordinate bonds were performed using density functional theory at B3LYP level. The calculated BDE values are 23.8, 25.5, 20.0, 22.3, 19.8 and 18.2 kcal/mol for 1, 2, 3, 4, 5 and 6, respectively. The BDE values suggest that the long Mn―O bonds in 1 and the long Co―O bonds in 3 are significantly weaker than their significantly shorter counterparts in the formerly reported [Mn(NiL)2(NCS)2] and [Co(NiL)2(NCS)2], respectively.All the M(II) centres (M = Mn, Fe, Co, Ni, Cu or Zn) in the six complexes adopt coordination environments featuring eightfold oxygen coordination and all the M―O bonds being abnormally long.Display Omitted► The six complexes have centres adopting unprecedented coordination environments. ► All the M―O bond distances are abnormally long. ► M(II) centres having the high coordination number of 8 often form long M―O bonds. ► Complexes with weak coordination environments would present different properties. ► The BDEs suggest that the long M―O bonds in 1–6 are significantly weak.
Keywords: Syntheses; DFT; BDE; Eight-semi-coordinate complexes;

N-arylation of imidazole was accomplished with a two-dimensional (2D) [Cu(ima)2]n metal–organic framework in methanol at room temperature. A variety of N-arylimidazoles were isolated in good yields after a short reaction time. Moreover, the robust MOF may be readily recovered after the reaction and reused for many cycles without loss of catalytic activity. N-Arylation of imidazole was accomplished with a robust two-dimensional metal–organic framework.Display Omitted► A simple 2D-CuMOF catalyst for N-arylation of imidazole has been developed. ► Unsaturatedly coordinated Cu2 + ions serve as catalytic centers. ► The catalyst may be easily reused for many cycles without loss of catalytic activity.
Keywords: N-arylation; Imidazole; Arylboronic acids; Metal–organic framework;

trans-Bis[1-(2-phenoxy)-imidazol-2-ylidene-C 2,O]platinum(II) complex bearing a dodecamethylene bridge (1) was synthesized and characterized by 1H, 13C NMR, COSY, NOESY, FT-IR, high-resolution mass spectroscopy, and single crystal X-ray diffraction. X-ray and 2D-NMR analyses revealed that complex 1 has a characteristic syn-conformation in both the solid and solution states, where cofacial phenoxy-NHC ligands are folded and fixed under strong restriction by the vaulted structure. A crystal of 1 obtained from EtOH exhibits weak blue phosphorescence under UV excitation at 320 nm.The first trans-bis[1-(2-phenoxy)-imidazol-2-ylidene-C 2,O]platinum(II) complex (1) was synthesized by utilizing high conformational restriction due to the vaulted structure. Complex 1 has a characteristic syn-conformation in both the solid and solution states, where cofacial phenoxy-NHC ligands are folded and fixed under strong restriction by the vaulted structure.Display Omitted► The first trans-ligating bis(o-phenoxy-NHC)Pt(II) complex ► Vaulted structure with polymethylene spacer ► Extremely syn-bent conformation maintained in both the solid and solution states
Keywords: Platinum(II); Vaulted complex; Carbene complex; Solid-state emission;

Single-ion magnet behavior of a new mononuclear dysprosium complex by Zhi-Gang Wang; Jing Lu; Chun-Yan Gao; Chao Wang; Jin-Lei Tian; Wen Gu; Xin Liu; Shi-Ping Yan (127-130).
A new mononuclear dysprosium complex formulated as [Dy(dppz) (tfnb)3]·0.375H2O (dppz = dipyrido[3,2-a:2′,3′-c]phenazine; tfnb = 4,4,4-trifluoro-1-(2-naphthyl)-1,3- butanedione) was synthesized, structurally and magnetically characterized. X-ray diffraction study reveals that the central DyIII ion in the complex adopts an approximately square-antiprismatic (SAP) geometry. The complex shows frequency-dependent ac magnetic susceptibilities, indicating single-ion magnet behavior.We have synthesized and structurally characterized a new mononuclear complex, which shows typical single-ion magnet behavior.Display Omitted► We synthesized a new dysprosium complex with its crystal structure characterized. ► Dc and ac magnetic susceptibilities of the complex were studied. ► The complex shows typical single-ion magnet behavior. ► The thermal activated relation energy barrier of the complex up to 65 K.
Keywords: Dysprosium; Crystal structure; Magnetic property; Single-ion magnet;

Design and synthesis of two macrocyclic dinuclear copper(II) complexes with reversible binding of nitric oxide by Yunfeng Chen; Huiting Song; Jiawei Mao; Ming Liu; Chao Ding; Zhiquan Pan (131-137).
Two new macrocyclic dinuclear copper(II) complexes, [Cu2L1(MeOH)2]·(ClO4)2 (1) and [Cu2L2(EtOH)2]·(ClO4)2 (2) have been synthesized and characterized by ES-MS spectra and X-ray crystallography determination. The coordination polyhedron of Cu(II) ions in each complex can be described as approximately square pyramind, where the apical position is occupied by a labile coordinated alcoholic molecule. The reactions of complexes with nitric oxide (NO) cause an immediate color change, and the formation of NO complexes has been further confirmed by UV/Vis spectrophotometry. The binding constants are calculated to be 1.71 × 103  M− 1 and 2.0 × 103  M− 1 in 0.2 M anaerobic phosphate buffer solution (PBS), respectively. The control experiments reveal that the binding of NO to complexes is reversible. Moreover, the interactions of the complexes with calf thymus DNA (CT-DNA) have been measured by UV/Vis, cyclic voltammetry and viscosity study. The moderate binding ability and unobvious DNA cleavage ability account for their low toxicity towards DNA. Overall, the results reveal that these two complexes can be served as potential NO regulators.The introduction of 2-pyridinylmethyl functional pendant arms induces a torsion of macrocycles in the template-directed synthesis, and the resulted copper(II) complexes bear labile coordinated alcoholic molecules, and show a reversible nitric oxide (NO) binding ability. Moderated DNA binding and inconspicuous DNA cleavage ability reveal these two complexes to be suitable for NO regulators.Display Omitted► Two macrocyclic dinuclear Cu(II) complexes have been designed and synthesized. ► Their central Cu(II) ions can bind to NO molecules reversibly. ► The complexes show good stability and good solubility. ► The complexes show inconspicuously DNA cleavage ability. ► These two complexes can serve as potential NO regulators.
Keywords: Copper(II); Macrocyclic complex; Nitric oxide regulator; DNA cleavage;

Synthesis and characterization of osmium(II) chlorocarbonyl complexes with bidentate phosphines by Anna Kamecka; Andrzej Kapturkiewicz; Zbigniew Karczmarzyk; Waldemar Wysocki (138-141).
Simple reactions of K2OsCl6 with a cis-1,2-bis(diphenylphosphino)ethene or 1,2-bis(diphenylphosphino)benzene in 1:2.05 ratio performed in refluxing DMF solution lead to the formation of the osmium(II) complexes with formulae of Os(P ∩ P)(CO)2Cl2. The obtained complexes were characterized by means of IR and 31P NMR spectroscopic techniques and their molecular structures were confirmed by X-ray investigations. Due to lability of CO and Cl within Os(P ∩ P)(CO)2Cl2 molecules both of the investigated complexes can be converted to luminescent [Os(N ∩ N)(P ∩ P)(CO)Cl]+ species.Simple reactions of K2OsCl6 with a cis-1,2-bis(diphenylphosphino)ethene or 1,2-bis(diphenylphosphino)benzene in 1:2.05 ratio performed in refluxing DMF solution lead mainly to the formation of the osmium(II) complexes with formulae of Os(P ∩ P)(CO)2Cl2. Due to lability of CO and Cl within Os(P ∩ P)(CO)2Cl2 molecules, these complexes can be converted to various luminescent species.Display Omitted► Os(P∩P)(CO)2Cl2 complexes can be prepared from K2OsCl6 and bidentate phosphines. ► Os(P∩P)(CO)2Cl2 species have been characterized using 31P NMR and IR spectroscopy. ► Os(P∩P)(CO)2Cl2 structures have been confirmed by means of X-ray investigations. ► Os(P∩P)(CO)2Cl2 can be converted to luminescent Os(P∩P)(N∩N)(CO)Cl+ chelates.
Keywords: Osmium(II) complexes; X-ray crystallography; 31P NMR spectroscopy; IR spectroscopy;

Iron(III) complexes of the metalloligand [Pt2(μ-S)2(PPh3)4] by William Henderson; Allen G. Oliver; Mark M. Turnbull (142-145).
Reaction of [Pt2(μ-S)2(PPh3)4] with (NH4)2SO4·FeSO4·6H2O and 2 mol equivalents of picolinic acid (HPic) or 8-hydroxyquinoline (HQ) and trimethylamine base gives iron(III) adducts [Pt2(μ-S)2(PPh3)4FePic2]+ and [Pt2(μ-S)2(PPh3)4FeQ2]+, isolated as hexafluorophosphate salts; these complexes are the first isolated iron(III) derivatives of [Pt2(μ-S)2(PPh3)4]. The X-ray structure of [Pt2(μ-S)2(PPh3)4FePic2]PF6 shows the presence of a rare distorted trigonal prismatic coordination geometry while magnetic measurements confirm the presence of high-spin iron(III) centres in the complexes.The first isolated iron(III) adducts of the dinuclear platinum(II) sulfido metalloligand are reported; the X-ray structure of the picolinate complex [Pt2(μ-S)2(PPh3)4FePic2]PF6 shows the presence of a rare distorted trigonal prismatic coordination geometry at iron, and magnetic measurements confirm the presence of a high-spin iron(III) centre. The corresponding complex containing deprotonated 8-hydroxyquinoline ligands is also described.Display Omitted► Synthesis of the first isolated iron complexes of [Pt2(m-S)2(PPh3)4]. ► Methodology involved air-oxidation of Fe(II) derivatives, monitored by ESI MS. ► X-ray structure shows coordination at Fe to be distorted towards trigonal prismatic. ► Magnetic measurements confirm high-spin iron(III).
Keywords: Platinum complexes; Iron complexes; Electrospray ionisation mass spectrometry; Crystal structure;

Two new Cd(II) coordination polymers, namely [Cd2(ipa)2(bib)1.5]n (1; H2ipa = isophthalic acid and bib = 1,4-bis(1-imidazol-yl)-2,5-dimethyl benzene) and {[Cd2(bpdc)2(bib)2]·5H2O}n (2; H2bpdc = biphenyl-4,4′-dicarboxylate), were prepared by the assemble of Cd2 +, dicarboxylate and bib ligands. Complex 1 shows a three-dimensional (3D) framework with 7-connected topological net, which can be viewed as constructing by linking two-fold interpenetrating pcu net. Complex 2 features a 3D 2-fold pcu topological net.Complex 1 shows a three-dimensional (3D) framework with 7-connected topological net, which can be constructed by linking two-fold interpenetrating pcu net.Display Omitted► The two Cd(II) coordination polymers are constructed by hydrothermal method. ► Complexes 1 and 2 display the different topological nets. ► The PL spectra of two complexes are also investigated.
Keywords: Crystal structure; Cadmium; Topology;

New chiral Sr(II) coordination polymer constructed from achiral 1,3,5-benzenetricarboxylic acid by Jia-Jia Niu; Chen Chen; Chang-Wen Ye; Xin Zhang; Yuan-Gen Yao; Lian-Fang Chen (149-151).
A new chiral Sr(II) compound, namely [Me2NH2]2n [Sr5(BTC)4(H2O)5] n (1 H3BTC = 1,3,5-benzenetricarboxylic acid), has been synthesized from achiral BTC ligands and corresponding metal salt. Single-crystal X-ray diffraction analysis revealed that it crystallized in the chiral space group C2221 and is a three-dimensional (3D) pillar-layered framework consisting of interesting crown-like tetranuclear [Sr4(COO)6(O1w)] clusters, which is rarely reported in the alkaline-earth metal coordination polymers. Moreover, this compound exhibits strong ligand-centered blue luminescence at room temperature.Presented here is a new chiral Sr(II) coordination polymer, [Me2NH2]2n [Sr5(BTC)4(H2O)5] n (1 H3BTC = 1,3,5-benzenetricarboxylic acid), constructed from achiral BTC ligand, which features an interesting crown-like tetranuclear [Sr4(COO)6(O1w)] cluster.Display Omitted► (i) A new chiral Sr(II) coordination polymer was constructed from achiral H3BTC ligand. ► (ii) It features a interesting crown-like tetranuclear [Sr4(COO)6(O1w)] cluster. ► (iii) It exhibits strong ligand-centered blue luminescence.
Keywords: Chiral; Compound/Tetranuclear; Cluster/Pillar-layered; Framework/Luminescence;

We discuss here the chemical oxidation of a high-spin iron(II) complex containing the 1,3-bis(2′-benzimidazolylimino)isoindoline ligand (HL1) using tris(4-bromophenyl)aminium hexachloroantimonate (Magic Blue). The product was X-ray structurally, spectroscopically (Mössbauer, FT-IR, UV–vis) and electrochemically characterized and can be formulated as [FeIII(L1)2][FeIII(L1H− 2)(L1)] (1), a low-spin iron(III) 1D coordination polymer with strong H-bonds between ligands and N,N-dimethylformamide (DMF) solvent molecules in the solid phase. The redox potential of the [FeII(L1)2] complex at − 407 mV vs. ferrocene in DMF is shifted to the anodic direction only by 12 mV in the case of 1 against the expected cathodic shift upon proton loss from the ligand. The difference in the spin state of [FeII(L1)2] and 1, and the impact of H-bonds (detected in the crystal structure) that are able to facilitate proton-coupled electron transfer have been considered as plausible explanations.High-spin to low-spin change upon 1e-oxidation and ligand deprotonation of a Fe(II) complex to the Fe(III) counterpart are involved in shift of E° value against the expected trend.Display Omitted► Deprotonation of the ligand upon oxidation of an octahedral, high-spin Fe(II) complex. ► Spin state changes to yield low-spin Fe(III) 1D coordination polymer (solid phase) ► ΔE° and ΔpKa shift against expected trands. ► H-bonds (PCET) and change in spin state are plausible explanations.
Keywords: Iron; Redox chemistry; Isoindoline; Oxidation; Mössbauer; Proton-coupled electron transfer;

Metal-organic coordination polymers have attracted an increasing level of research attention in the scientific community, while the study of these materials in a confined space could also help industrial engineers to anticipate new properties. A novel 1D luminescent zinc(II) coordination polymer {[Zn(μ-dca)(4,4′-azpy)2(H2O)2]ClO4}n (1, dca = dicyanamide; 4,4′-azpy = trans-4,4′-azobis(pyridine)) has been synthesized and subsequently encapsulated in the nanoporous material MCM-41 in this work. For confined 1, the bathochromic shift of the 0–0 transitions has been correlated with the reduced HOMO–LUMO band gap accompanying with the increased energies of the frontier molecular orbitals.This paper reports the preparation of a luminescent zinc(II) coordination polymer, its encapsulation in the nanoporous material MCM-41, and property investigation of this nanocomposite system.Display Omitted► A novel 1D luminescent zinc(II) coordination polymer. ► Encapsulation of this zinc(II) coordination polymer in the nanoporous channels. ► Experimental and theoretical investigation of the properties of this system.
Keywords: Zinc; Coordination polymer; Luminescence; Nanoporous material;

6-(Thien-2-yl)-2,2′-bipyridine: Presenting an N^N or N^N^S donor set to silver(I) by Edwin C. Constable; Catherine E. Housecroft; Peter Kopecky; Markus Neuburger; Jennifer A. Zampese (159-162).
Reaction of two equivalents of 6-(thien-2-yl)-2,2′-bipyridine (1) with AgPF6 in CH2Cl2 produces the mononuclear complex [Ag(1)2][PF6] in which the Ag+ ion is in a flattened-tetrahedral Ag(N^N)2-environment in the solid state; the thiophenyl substituents are not coordinated. When equal equivalents of AgPF6 and 1 react in CH2Cl2, a mixture of [Ag(1)2][PF6] and {2[Ag3(1)4][PF6]3 ·3H2O} n is formed. Single crystal X-ray diffraction confirms that {2[Ag3(1)4][PF6]3 ·3H2O} n is a coordination polymer, with a helical arrangement of ligands enveloping a chain of silver(I) ions. Distances between adjacent pairs of Ag atoms are 3.087(1), 3.884(1) and 4.763(1) Å, with only one in three pairs exhibiting argentophilic interaction.6-(Thien-2-yl)-2,2′-bipyridine (1) reacts with AgPF6 to yield [Ag(1)2][PF6], or [Ag(1)2][PF6] and {2[Ag3(1)4][PF6]3 ·3H2O} n depending on stoichiometry of the reaction. Single crystal X-ray diffraction confirms that in [Ag(1)2]+, 1 behaves as an N^N chelate; {2[Ag3(1)4][PF6]3 ·3H2O} n is a coordination polymer in which 1 acts as an N^N^S donor connecting Ag+ ions into one dimensional chains.Display Omitted► Reaction of 6-(thien-2-yl)-2,2′-bipyridine (1) with AgPF6. ► Competitive formation of mononuclear [Ag(1)2]+ and polymeric {[Ag3(1)4]}n 3n+.
Keywords: Silver(I); 2,2′-Bipyridine; Thiophene; Crystal structure; Coordination polymer;

Ring-opening of tetrahydrofuran with PCl3 catalysed by an ortho-xylidenedizinc complex by Thomas Albers; Peter G. Edwards; Paul D. Newman (163-165).
The reaction of 1,2-o-xylyl dichloride with activated zinc in THF gives the organozinc compound [(μ-o-xyl)Zn2Cl2(THF)4], 1, where xyl = (2-methanidylphenyl)methanide. The compound is stable in the solid state but undergoes a slow decomposition in solution to generate the μ4-oxo cluster [(μ-o-xyl)2Zn4(μ-Cl)24-O)(THF)4], 3, which has been characterised in the solid state by single-crystal X-ray techniques. The organozinc complex 1 catalyses the ring-opening of THF in the presence of PCl3 to give a mixture of the two compounds [Cl(CH2)4O]PCl2 and [Cl(CH2)4O]2PCl.An ortho-xylidenedizinc compound catalyses the room temperature ring-opening of THF by PCl3 to give 4-chlorobutyl phosphorodichloridoite and bis(4-chlorobutyl)phosphorochloridoite. The reaction occurs within minutes at room temperature using 20% of the organozinc compound.Display Omitted► A new o-xylidenedizinc complex has been synthesised. ► The complex abstracts oxygen from THF on standing to give a μ4-oxo tetrazinc cluster. ► The organozinc compound catalyses the ring-opening of THF with PCl3.
Keywords: Organozinc; Ring-opening; μ4-Oxo; Phosphorus trichloride; THF-cleavage;

Three cobalt (II) complexes with triethylenetetraaminehexaacetic acid: From binuclear complex to 3d-4f coordination polymers by Yan Ouyang; Cheng-Zhi Xie; Jing-Yuan Xu; Li Yu; Mei-Ling Zhang; Dai-Zheng Liao (166-170).
The cobalt(II)–lanthanide(III) heteronuclear complexes [Ln(H2O)4Co2(TTHA)(SCN)2]·H3O+ (H6TTHA = triethylenetetraaminehexaacetic acid, Ln = La(2), Ce(3)) have been synthesized based on a binuclear building block of [Co2(H2TTHA)(H2O)2] in [Co2(H2TTHA)(H2O)2]·4H2O (1). Single-crystal structures show that complex 1 is a binuclear complex, containing the [Co2(H2TTHA)(H2O)2] unit as a useful building block. Adding the La3 + and Ce3 + ions to this synthesis system, two new 3d-4f mixed complexes 2 and 3 were obtained. Complexes 2 and 3 show 3D framework, comprising an infinite 1D (one-dimensional) chain based on heterometallic Ln2Co2 (Ln = La(2), Ce(3)). Further investigations such as IR spectra, UV–vis spectra, TGA, XRD and magnetic properties were studied.Three novel complexes [Co2(H2TTHA)(H2O)2]·4H2O (1), [Ln(H2O)4Co2(TTHA)(SCN)2]·H3O+ (H6TTHA = triethylenetetraaminehexaacetic acid, Ln = La(2), Ce(3)) were synthesized and characterized. Complex 1 is a binuclear complex, while complexes 2 and 3 show 3D framework, comprising an unusual infinite 1D chain based on heterometallic Ln2Co2 (Ln = La(2), Ce(3)).Display Omitted► Three novel complexes with H6TTHA have been synthesized and characterized. ► Complex 2 and 3 are 3d-4f coordination polymers with 3D framework. ► The 3D framework comprise an infinite 1D chain based on heterometallic Ln2Co2. ► This report provides an available way of the construction of 3d-4f complexes.
Keywords: Triethylenetetraaminehexaacetic acid; 3d-4f coordination polymers; 3D framework; Magnetic properties;

Synthesis, crystal structure and characterization of new tetranuclear Ag(I) complex with 5-aminoisophthalate by Xiao-Wu Lei; Fang-Xia Zhou; Ming-Feng Wang; Hui-Ping Zhang; Cheng-Yang Yue; Mao-Chun Hong (171-174).
One new AgI complex, [Ag2(aip)(NH3)]n (H2aip = 5-aminoisophthalic acid), has been prepared and structurally and spectroscopically characterized. The title complex crystallizes in the monoclinic system P21/c (no. 14) with a  = 6.975(2) Å, b  = 8.756(3) Å, c  = 16.086(6) Å, β  = 97.318(4)°, V = 974.4(6) Å3 and Z = 4. Its structure features a three-dimensional (3D) network composed of two-dimensional (2D) flexuous layer interconnected via weak hydrogen bonds. In aqueous solution, the H2aip exhibits blue emission, while the title complex with tetranuclear silver(I) cores and weak Ag…Ag bonds shows visible intense purple luminescence.One new silver(I) complex [Ag2(aip)(NH3)]n has been synthesized and structurally characterized. The complex features 3D network built from 2D flexuous layer containing tetranuclear silver(I) core. In the aqueous solution state, the H2aip can give strong blue emission, whereas the complex 1 exhibits strong purple luminescence at room temperature.Display Omitted► Synthesis of one new AgI complex with tetranuclear silver(I) cores. ► Complex exhibits visible intense purple luminescence at room temperature. ► Complex shows strong green emission at 77 K.
Keywords: Coordination polymer; Ag(I); Argentophilicity; H2aip; Luminescence;