Inorganic Chemistry Communications (v.11, #6)

Contents List (iii-x).

Bis(2,2′-bipyridine)ruthenium(II) complexes of two chelating ligands containing [1,2,3]triazolo[1,5-a]pyridine subunits have been prepared. X-ray crystal structures show that this ring system remains intact upon coordination to ruthenium. Spectroscopic and electrochemical data reflect the electron-rich nature of these ligands.Bis(2,2′-bipyridine)ruthenium(II) complexes of two chelating ligands containing [1,2,3]triazolo[1,5-a]pyridine subunits have been prepared. X-ray crystal structures show that this ring system remains intact upon coordination to ruthenium. Spectroscopic and electrochemical data reflect the electron-rich nature of these ligands.
Keywords: Ruthenium; Triazolopyridine; Crystal structure; N ligands;

A single-source precursor route to antimony sulpho-iodide by Gabriele Kociok-Köhn; Kieran C. Molloy; Jorge Rodriguez-Castro (599-603).
Antimony sulpho-iodide has been synthesised from the single-source precursor S(CH2CH2S)2SbI by a novel intra-molecular decomposition pathway which involves elimination of 1,4-dithiane whilst preserving the weak Sb–I bond.Antimony sulpho-iodide has been synthesised from the single-source precursors S(CH2CH2S)2SbI or (CH2S)2SbI by a novel intra-molecular decomposition pathway which involves elimination of 1,4-dithiane whilst preserving the weak Sb–I bond. Both precursors have been characterised by X-ray crystallography.
Keywords: Antimony; Sulpho-iodide; Ferroelectric; Single-source precursor; X-ray crystallography;

Hydrothermal reaction of lead(II) acetate with diphosphonate Hedp (Hedp = l-hydroxyethylidene diphosphonate) yield a new lead(II) phosphonate, Pb[(PO3)2C(OH)CH3] · H2O (1). Complex 1 has a two-dimensional double layered hybrid structure containing interconnected 4- and 12-membered rings and shows an unusual (5,5)-connected (47  · 63) (48  · 62) topology.A new lead(II) phosphonate, Pb[(PO3)2C(OH)CH3] · H2O (1) was hydrothermally synthesized and characterized by IR, elemental analysis, UV, TGA, SEM, and single crystal X-ray diffraction analysis. X-ray crystallographic study showed that complex 1 has a two-dimensional double layered hybrid structure containing interconnected 4- and 12-membered rings and shows an unusual (5,5)-connected (47  · 63) (48  · 62) topology.
Keywords: Lead phosphonate; Crystal structure; Layered structure; Topology;

A novel zinc complex diaminebis(phenolate) [zinc 2,2-{μ-(N-N′-dimethylethyleneamino)dimethyl}-bis(4,6-di-tert-butylphenolate)] (LZn) was synthesized, structurally characterized, and its application as an initiator for the ring-opening polymerization of rac-lactide was reported.A novel zinc complex diaminebis(phenolate) [zinc 2,2-{μ-(N,N′-dimethylethyleneamino)dimethyl}-bis(4,6-di-tert-butylphenolate)] (LZn) was synthesized, structurally characterized, and its application as an initiator for the ring-opening polymerization of rac-lactide was reported.
Keywords: Zinc complex; rac-Lactide; Polymerization;

Reaction of [(tmeda)NiMe2] with 2-pyridylmethylamine and (2-pyridylmethyl)(diphenylphosphanyl)amine by Astrid Malassa; Helmar Görls; Matthias Westerhausen (612-615).
(TMEDA)NiMe2 undergoes a variety of different reactions which include (i) reductive elimination of ethane, (ii) substitution of TMEDA by other bidendate amines. A combination of both these reactions leads to the formation of the nickel(0) complex Ni[P(Ph2)–N(H)–CH2Py]4.2-Aminomethylpyridine (Amp) substitutes the bis(dimethylamino)ethane ligand (TMEDA) of [(tmeda)NiMe2] leading to the formation of N,N′-(2-aminomethylpyridine)dimethylnickel (1). The reaction of bulkier N-diphenylphosphanyl-2-aminomethylpyridine with [(tmeda)NiMe2] yields tetrakis(N-diphenylphosphanyl-2-aminomethylpyridine)nickel(0) (2), ethane and TMEDA. The nickel(II) complex 1 shows a distorted square planar environment for the metal center, whereas nickel(0) in 2 displays a distorted tetrahedral coordination sphere with an average Ni–P bond length of 217.35 pm.
Keywords: Nickel; Dimethylnickel; Phosphane complexes; Amine complexes;

Two novel forms of uranyl formate assemblages were obtained, the first an H-DABCO+-templated ribbon architecture and the second a nanotubular material with an inner tubule diameter of ca. 6 Å.Reaction of uranyl nitrate with formic acid in the presence of DABCO or NMe4OH under hydrothermal conditions gave two novel uranyl-organic frameworks. When templated by H-DABCO+ counter-ions, uranyl formate crystallizes as ribbons including μ3-oxo and μ2- and μ3-hydroxo ions. In one experiment with NMe4OH, a nanotubular material was obtained instead of the more usual two- or three-dimensional uranyl formates, with an inner tubule diameter of ca. 6 Å.
Keywords: Uranyl ion; Uranyl-organic framework; Nanotubules; Formic acid; Hydrothermal synthesis;

Characterization of a well-resolved water layer containing (H2O)40 water morphology via dianion templating by Ya-Pan Wu; Feng Fu; Dong-Sheng Li; Zhen-Hua Yang; Kun Zou; Yao-Yu Wang (621-625).
A well-resolved 2D supramolecular water layer, which self-assembled by (H2O)40 water morphology via templating with tartrate dianion, has been observed in the compound [Cu2(tar)(2,2′-bipy)4]tar · 12H2O(1) [tar = tartrate dianion]. Hydrogen bonding interactions between the 2D layers of water and binuclear moieties create a unique, infinite supramolecular edifice.A well-resolved 2D supramolecular water layer, which self-assembled by (H2O)40 water morphology templating via tartrate dianion, has been observed in the compound [Cu2(tar)(2,2′-bipy)4]tar · 12H2O(1) [tar = tartrate dianion]. Hydrogen bonding interactions between the 2D layers of water and binuclear moieties create a unique, infinite 3D supramolecular edifice.
Keywords: Copper(II) compound; Supramolecular assembly; Water layer; Hydrogen bond; Template effect;

Highly selective colorimetric sensor for Zn2+ based on hetarylazo derivative by Paramjit Kaur; Sandeep Kaur; Aman Mahajan; Kamaljit Singh (626-629).
An intensely colored hetarylazo derivative 1 demonstrates a highly selective color change from red to faint orange upon Zn2+ sensing and demonstrates very high Zn2+ over Cd2+ selectivity.An intensely colored hetarylazo derivative 1 possessing thiadiazole derivative as diazo component and m-aminoacetanilide based coupling component has been synthesized and demonstrates a highly selective color change from red to faint orange upon sensing of Zn2+. Other cations of the same group; Cd2+ did not interfere in the sensing process; however, Hg2+ interfered only at very high concentrations but depicted interesting sensing behaviour of its own. Other commonly occurring cations such as Ca2+, Mg2+ and Cu2+ did not respond to the sensing event. The pH stability of the azo derivative offers additional advantage in the sensing process.
Keywords: Hetarylazo dye; Colorimetric sensing; Chemosensor; Cation sensing; Zinc sensing;

The new soluble metal-free and Ni(II), Zn(II), Co(II), Cu(II), Pb(II) phthalocyanines with four tetrathiamacrocycles were obtained from 4-[(11-hyroxy-1,5,9,13-tetrathiacyclohexadecan-3-yl)oxy]phthalonitrile 3 and the corresponding divalent metal salt (NiCl2, Zn(CH3COO)2, CoCl2, CuCl2 and PbO). Metal-free and metallophthalocyanines showed an enhanced solubility in organic solvents. The structures of the target compounds were confirmed using elemental analysis, IR, 1H NMR, 13C NMR, UV–vis and MS spectral data.The new soluble metal-free and Ni(II), Zn(II), Co(II), Cu(II), Pb(II) phthalocyanines with four, tetrathiamacrocycles were obtained from 4-[(11-hyroxy-1,5,9,13-tetrathiacyclohexadecan-3-yl)oxy]phthalonitrile 3 and the corresponding divalent metal salt (NiCl2, Zn(CH3COO)2, CoCl2, CuCl2 and PbO). Metal-free and metallophthalocyanines showed the enhanced solubility in organic solvents. The structures of the target compounds were confirmed using elemental analysis, IR, 1H NMR, 13C NMR, UV–vis and MS spectral data.
Keywords: Tetrathiamacrocycles; Metallophthalocyanine; Synthesis; Microwave; Phthalonitrile;

The synthesis and characterization of new metal-free (4) and metallophthalocyanines (5, 6, 7 and 8) substituted four 15-membered tetraoxamonoaza macrocycles from 7-[(4-methylphenyl)sulfonyl]-2,3,6,7,8,9,11,12-octahydro-5H-1,4,10,13,7-benzotetraoxazacyclopen tadecine-15,16-dicarbonitrile (3) is described. The new compounds were characterized by a combination of IR, 1H NMR, 13C NMR, UV–vis, elemental analysis and MS spectral data.The synthesis and characterization of new metal-free (4) and metallophthalocyanines (5, 6, 7 and 8) substituted four 15-membered tetraoxamonoaza macrocycles from 7-[(4-methylphenyl)sulfonyl]-2,3,6,7,8,9,11,12-octahydro-5H-1,4,10,13,7- benzotetraoxazacyclopen tadecine-15,16-dicarbonitrile (3) is described. The new compounds were characterized by a combination of IR, 1H NMR, 13C NMR, UV–vis, elemental analysis and MS spectral data.
Keywords: Phthalocyanine; Tetraoxamonoazamacrocycle; Phthalonitrile; Macrocyclization; Metallophthalocyanine;

Two coordination compounds namely [{(H2O)2(NO3)4(MeOH)2Cd2(μ-L1)2}] 1 and [{(H2O)2Cd(μ-SO4)(μ-L1)}] n 2 have been isolated by reacting a bis-pyridyl-bis-amide ligand namely N,N′-bis-(3-pyridyl)isophthalamide L1 with Cd(NO3)2 and CdSO4, respectively. Single crystals of both 1 and 2 were determined. It was revealed from the X-ray analyses that conformation dependent ligating topology of L1 and different coordination modes of the counter anions (nitrate and sulfate) are responsible for the formation of discrete metallo-macrocycle (compound 1) and 2D corrugated sheet (compound 2).Two coordination compounds namely [{(H2O)2(NO3)4(MeOH)2Cd2(μ-L1)2}] 1 and [{(H2O)2Cd(μ-SO4)(μ-L1)}] n 2 have been isolated by reacting a bis-pyridyl-bis-amide ligand namely N,N′-bis-(3-pyridyl)isophthalamide L1 with Cd(NO3)2 and CdSO4, respectively. Single crystals of both 1 and 2 were determined. It was revealed from the X-ray analyses that conformation dependent ligating topology of L1 and different coordination modes of the counter anions (nitrate and sulfate) are responsible for the formation of discrete metallo-macrocycle (compound 1) and 2D corrugated sheet (compound 2).
Keywords: Crystal engineering; MOFs; Ligating topology; Anion control; X-ray crystallography;

A new μ-oxo di-iron complex with suitable features to mimic metallohydrolase activity: X-ray molecular structure, aqua solution behavior and nuclease activity of the complex [Fe(HPClNOL)(SO4)]2-μ-oxo by Gabrieli L. Parrilha; Christiane Fernandes; Adailton J. Bortoluzzi; Bruno Szpoganicz; Marlon de S. Silva; Claus Tröger Pich; Hernán Terenzi; Adolfo Horn (643-647).
Complex [Fe(HPClNOL)(SO4)]2-μ-oxo successfully promotes the hydrolytic cleavage of plasmid DNA, producing single and double DNA strand breaks at very low concentrations and at physiological pH.The reaction of FeSO4  · 7H2O with the ligand HPClNOL (1-(bis-pyridin-2-ylmethyl-amino)-3-chloropropan-2-ol results in the complex [Fe(HPClNOL)(SO4)]2-μ-oxo · 6H2O 1, in which the iron ions are coordinated by two pyridines, one amine and one alcohol group from the ligand HPClNOL, an oxo bridge and monodentate sulfate ion. The complex is highly soluble in water and potentiometric titration experiments reveal four protonation/deprotonation equilibria, with pK a values of 2.77(3), 4.34(6), 8.07(4) and 8.58(8). The nuclease activity of complex 1 was evaluated at pH 7.0, 8.0 and 9.0. Complex 1 was able to promote single and double strand DNA cleavage in both aerobic and anaerobic condition, indicating that the cleavage process should follow a hydrolytic mechanism.
Keywords: DNA cleavage; Hydrolysis; Potentiometric titration; Di-iron complex; Nuclease activity;

A new molybdenum arsenate compound [{Cu(imi)2}3As3Mo3O15] · H2O (1), has been hydrothermally synthesized and structurally characterized for first time. Compound 1 is observed firstly of molybdenum arsenate fragment as polydentate ligand covalently bonded to three [CuI(imi)2] complexes through Ob⋯Ot⋯Ob atoms.A novel molybdenum arsenate compound [{Cu(imi)2}3As3Mo3O15] · H2O (imi = imidazole) 1, has been prepared by hydrothermal method and structurally characterized by elemental analysis, IR, XPS, TG analysis and single-crystal X-ray diffraction analysis. Compound 1 represents the first example of molybdenum arsenate fragment [As3Mo3O15]3− as polydentate ligand covalently bonded to three [ Cu I ( imi ) 2 ] complexes through Ob⋯Ot⋯Ob (Ot, terminal oxygen; Ob, bridging oxygen) atoms. The electrochemical behavior and electrocatalysis of 1-modified carbon paste electrode (CPE) have been studied in detail.
Keywords: Molybdenum arsenate; Copper-complex; Electrochemical properties;

Trapping and crystallographic characterization of Valsartan intermediate (tetrazole–zinc complex) by Guang-Fan Han; Guo-Xi Wang; Cheng-Jian Zhu; Ying Cai; Ren-Gen Xiong (652-654).
This is the first example of crystallographic characterization of Zn-complex with HMBT produced during in situ [2+3] cycloaddition between 4-methylbiphenyl-2-carbonitrile (MBC) and NaN3 in the presence of ZnCl2. Also, crystal structural determinations of HMBT and impurity produced during hydrothermal hydrolysis reaction of MBC were reported.4′-Methylbiphenyl-2-tetrazole (HMBT) is an important intermediate to the synthesis of Valsartan while HMBT is obtained by the decomposition of Zn-complex (organic–inorganic polymer) containing HMBT. This is the first example of crystallographic characterization of Zn-complex with HMBT produced during in situ [2+3] cycloaddition between 4-methylbiphenyl-2-carbonitrile (MBC) and NaN3 in the presence of ZnCl2. Also, crystal structural determinations of HMBT and impurity produced during hydrothermal hydrolysis reaction of MBC were reported.
Keywords: Valsartan intermediate; In situ [2+3] cycloaddition; Zn–tetrazole complex;

Magnetic coupling detected by EPR in a paddle-wheel copper(II) complex of the amino acid guanidinoacetic acid by Jussara Lopes de Miranda; Judith Felcman; Marcelo H. Herbst; Ney V. Vugman (655-658).
Interesting magnetic properties have been detected by EPR in a paddle-wheel carboxylate copper(II) complex of guanidinoacetic acid (GAA), Cu2(GAA)4(NO3)2 (tetrakis(μ-guanidinoacetic acid-κ2O:O′) bis[(nitrato-κO) copper(II)]). The variable temperature EPR study revealed an anti-ferromagnetic coupling between the two copper ions, an intradimer interaction, and an interdimer coupling, which was a temperature–driven interaction.Interesting magnetic properties of a paddle-wheel carboxylate bridged copper(II) complex of guanidinoacetic acid (GAA), Cu2(GAA)4(NO3)2 (tetrakis(μ-guanidinoacetic acid-κ2O:O′) bis[(nitrato-κO) copper(II)]) (I) were detected by electron paramagnetic resonance (EPR). The complex I contains two copper ions coordinated to four GAA ligands (d Cu–Cu 2.65 Å) through the oxygen atoms from the carboxylate group forming a paddle-wheel complex and a supramolecular assembly. The EPR data (40–300 K) revealed two distinct groups of lines. One of them is related to the intra-dimer coupling, an anti-ferromagnetic interaction between the copper ions. The other group of lines, which was only observed above 180 K, can be attributed to the inter-dimer coupling or pair formation.
Keywords: Paddle-wheel complex; Copper; Guanidinoacetic acid; Intra and interdimer interactions;

Unusual 2D assembly of the paddle wheel Cd2(COO)4 units in a luminescent complex by Yi-Hang Wen; Xia Feng; Yun-Long Feng; You-Zhao Lan; Yuan-Gen Yao (659-661).
A novel Cd(II) complex with unusual 2D assembly of the paddle wheel Cd2(COO)4 units, [Cd(μ5-1,8-nap)] n (1, 1,8-nap = naphthalene-1,8-dicarboxylate), has been hydrothermally synthesized. It displays strong blue fluorescent emission in the solid state.A novel Cd(II) complex with unusual 2D assembly of the paddle wheel Cd2(COO)4 units, [Cd(μ5-1,8-nap)] n (1,8-nap = naphthalene-1,8-dicarboxylate) (1), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, luminescent analysis and thermal analysis. It displays strong blue fluorescent emission in the solid state.
Keywords: Naphthalene-1,8-dicarboxylate; Cadmium complex; Hydrothermal synthesis; Luminescent property;

Synthesis, crystal structure and properties of a Zn(II) complex with a new N,N,O-tridentate chelate ligand by Shanji Li; Jiang Lu; Hui Liang; Shiliang Han; Xiang Zhou (662-664).
A Zn(II) complex with a new N,N,O-tridentate chelate ligand, namely 2-(benzimidazol-2-yl)-8-octyloxyquinoline, was synthesized. The crystal structure and properties of the complex were presented.A new N,N,O-tridentate chelate ligand, namely 2-(benzimidazol-2-yl)-8-octyloxyquinoline, has been synthesized with 8-hydroxyquinadine and o-phenylenediamine as the starting materials. The obtained ligand reacts with diethylzinc to give a neutral Zn(II) complex. The molecular structure of the complex has been determined by X-ray crystallography. The preliminary investigations on the thermal, electrochemical and luminescent properties of the complex are presented.
Keywords: Zinc complex; Benzimidazole; 8-Hydroxyquinadine; Molecular structure; Properties;

Dinuclear copper(II) trispyrazolylborate derivatives with bridging pyrazolate anions by Corrado Di Nicola; Fabio Marchetti; Magda Monari; Luciano Pandolfo; Claudio Pettinari (665-668).
Trispyrazolylborate (Tp) and tris(3,5-dimethyl)pyrazolylborate (Tp∗) partially break the trinuclear triangular core of the cluster [Cu33-OH)(μ-pz)3(MeCOO)2(Hpz)], generating dinuclear Cu(II) μ-pyrazolate compounds 2 and 3, having as capping κ 3 ligands Tp and Tp∗, respectively. The structure of 3 is strongly influenced by the steric encumbrance of the methyl substituents, that keeps the two Cu ions in 3 farther with respect to 2.Two μ-pyrazolate dicopper derivatives, [Cu2(μ-pz)2(Tp x )2] [Tp x  = Tp, tris(pyrazol-1-yl)borate or Tp∗, tris(3,5-dimethylpyrazol-1-yl)borate], prepared either by treating the trinuclear [Cu33-OH)(μ-pz)3(RCOO)2L x L′ y ] species (R = H, Me, Et, Pr; L, L′ = H2O, MeOH, EtOH, Hpz; Hpz = pyrazole) with an excess of M[Tp x ] (M = Na, K) or by reaction of Cu(RCOO)2 with equimolar amounts of Hpz and M[Tp x ], have been characterized by IR, magnetic susceptibility measurements and single crystal XRD structural determination.
Keywords: Dinuclear complexes; Copper(II); Pyrazolate complexes; Trispyrazolylborates; Crystal structure;

Phosphorescence of permercurated osmocene at ambient conditions by Horst Kunkely; Arnd Vogler (669-671).
The permercurated osmocene derivative Os[C5(HgOAc)5]2 shows a LF phosphorescence at λ max  = 770 nm at ambient conditions. This triplet emission is facilitated by the heavy-atom effect of mercury and, possibly, by the absence of C–H vibrations which may assist radiationless deactivation in osmocene.The permercurated osmocene derivative Os[C5(HgOAc)5]2 shows a LF phosphorescence at λ max  = 770 nm at ambient conditions. This triplet emission is facilitated by the heavy-atom effect of mercury and, possibly, by the absence of C–H vibrations which may assist radiationless deactivation in osmocene.
Keywords: Luminescence; Phosphorescence; Osmium; Mercury; Heavy-atom effect;

{[Cu2(μ-Cl)(μ-dppm)2](μ2-TCNQ)}, a charge transfer compound derived from a donor with a copper dimer by Yong-qin Song; Qi-ying Lv; Shu-zhong Zhan; Jian-ge Wang; Jia-yin Su; An Ding (672-674).
The reaction of CuCl, dppm (bis(diphenylphosphino)methane), and TCNQ with a molar ratio set of 2:2:1 produced a one-dimensional compound 1 {[Cu2(μ-Cl)(μ-dppm)2](μ2-TCNQ)}. Its structure was determined by X-ray crystallography. The new compound 1 was studied by IR and UV/Vis/NIR spectroscopy. 1 exhibits an intervalence transfer transition at λ  = 1296 nm, and also appears photoluminescence (λ max  = 818 nm) at room temperature.The reaction of CuCl, dppm (bis(diphenylphosphino)methane), and TCNQ with a molar ratio set of 2:2:1 produced a one-dimensional compound 1 {[Cu2(μ-Cl)(μ-dppm)2](μ2-TCNQ)}. Its structure was determined by X-ray crystallography. The new compound 1 was studied by IR and UV/Vis/NIR spectroscopy. 1 exhibits an intervalence transfer transition at λ  = 1296 nm, and also appears photoluminescence (λ max  = 818 nm) at room temperature.
Keywords: Copper dimer; Charge transfer; N ligands; Luminesence;

Nonadecanuclear Mn 7 II Mn 12 III cluster with a spin ground state of S  = 73/2 by Chun-Hua Ge; Zhong-Hai Ni; Cai-Ming Liu; Ai-Li Cui; De-Qing Zhang; Hui-Zhong Kou (675-677).
High-nuclearity cluster [ Mn 7 II Mn 12 III ( μ 4 -O ) 8 ( μ 1 , 1 , 1 - N 3 ) 8 ( Hhmmp ) 12 ( H 2 O ) 6 ] ( OH ) 2 · 22 H 2 O displays a spin ground state of 73/2.Reaction of Mn(ClO4)2  · 6H2O with 2,6-bis(hydroxymethyl)-4-methylphenol (H3hmmp) in the presence of sodium azide gives rise to a high-nuclearity cluster [ Mn 7 II Mn 12 III ( μ 4 -O ) 8 ( μ 1 , 1 , 1 - N 3 ) 8 ( Hhmmp ) 12 ( OH ) 2 ( H 2 O ) 4 ] · 24 H 2 O that displays a spin ground state as high as 73/2.
Keywords: Crystal structure; Mn complex; Azide bridge; Polynuclear; Magnetic properties;

The synthesis, X-ray structure and properties of a dinuclear nickel(II) complex of the triply deprotonated pentadentate Schiff base, N,N′-(2-hydroxypropane-1,3-diyl)bis(acetylacetoneimine) are reported.The synthesis and X-ray structure of a dinuclear nickel(II) complex of the triply deprotonated pentadentate Schiff base, N,N′-(2-hydroxypropane-1,3-diyl)bis(acetylacetoneimine) (apacaH3), are reported. The complex, which was obtained by reaction of apacaH3 with nickel acetate in ethanol, has a binuclear structure of type [Ni2 (apaca)(OAc)] in which each metal centre is bound to a deprotonated enolic oxygen and an imine nitrogen from an acetylacetoneimine ‘arm’ of apaca. The nickel centres are bridged by both an alkoxide oxygen derived from the 2-hydroxypropane unit in apaca and an acetato group. Each metal centre has a distorted square-planar geometry, with the overall configuration being non-planar. This complex is isostructural with a previously-reported, copper(II) complex of similar stoichiometry, prepared by an analogous procedure from copper(II) acetate. The present result contrasts with a previous report in which apacaH3 was claimed to interact with nickel(II) acetate in ethanol in the presence of potassium ethoxide to yield a square-planar complex of the corresponding doubly deprotonated Schiff base ligand.
Keywords: Nickel(II); Dinuclear; Schiff base; X-ray structure;

The isolation and properties of an unexpected cyano-bridged complex [(H2O)CoII(dppm)2(μ-CN)CoIICl3] · C2H5OH by Wei Li; Shu-zhong Zhan; Jian-ge Wang; Wen-yuan Yan; Yuan-fu Deng (681-683).
One reaction of CoCl2  · 6H2O, dppm (diphenylphosphinomethane), and TCNE (tetracyanoethylene) in C2H5OH solvent gave one unexpected cyano bridged complex [(H2O)CoII(dppm)2(μ-CN)CoIICl3] · C2H5OH 1. Compound 1 is built from Co(II) and Co(II) centers, which are bridged by one CN group. It was characterized by IR spectra, UV–Vis spectra, and cyclic voltammogram. It is worth noting that CoII ions in 1 exhibit thermally induced quartet ↔ doublet spin transitions, and there is an antiferromagnetic interaction between the adjacent CoII and CoII ions through the cyanide bridge in 1.One reaction of CoCl2  · 6H2O, dppm (diphenylphosphinomethane), and TCNE (tetracyanoethylene) in C2H5OH solvent gave one unexpected cyano-bridged complex [(H2O)CoII(dppm)2(μ-CN)CoIICl3] · C2H5OH 1. Compound 1 is built from Co(II) and Co(II) centers, which are bridged by one CN group. It was characterized by IR spectra, UV–Vis spectra, and cyclic voltammogram. It is worth noting that CoII ions in 1 exhibit thermally induced quartet ↔ doublet spin transitions, and there is an antiferromagnetic interaction between the adjacent CoII and CoII ions through the cyanide bridge in 1.
Keywords: P-ligand; Crystal structure; Cyano-bridged complex; Magnetic property;

The first diorganotin(IV) complex 1 with N′-acylsalicylhydrazide has been successfully synthesized and structurally characterized by elemental analysis, FT-IR, NMR (1H, 119Sn) spectra and X-ray crystallography. The complex 1 is an infinite 1D polymer with tetranuclear organotin(IV) as secondary building units, which contains five- and seven-coordinated two kinds of tin atoms.The first diorganotin(IV) complex 1 with N′-acylsalicylhydrazide has been successfully synthesized and structurally characterized by elemental analysis, FT-IR, NMR (1H, 13C and 119Sn) spectra and X-ray crystallography. The complex 1 is an infinite 1D polymer with tetranuclear organotin(IV) as secondary building units, which contains five- and seven-coordinated tin atoms.
Keywords: Diorganotin(IV); N′-acylsalicylhydrazide; Crystal structure; Coordination polymer;

Three novel bridging ligands and corresponding dinuclear Ru(II) complexes have been synthesized. These complexes exhibit abundant electrochemical properties, show characteristic MLCT absorption band at 445–453 nm and emission at 571–593 nm.Three polypyridyl bridging ligands cis-di(4,5-diazafluoren-9-ylimino)dibenzo-18-crown-6 (BL1), trans-di(4,5-diazafluoren-9-ylimino)dibenzo-18-crown-6 (BL2), and 1,4,7,10,13,16-hexaoxacycloctadecyl[2,3:11,12]bis-dipyrido[3,2-a:2′3′-c]phenazine (BL3), and corresponding dinuclear Ru(II) complexes [(bpy)2RuBL1−3Ru(bpy)2](PF6)4 (1, 2, and 3) have been synthesized. Cyclic voltammetry of the complexes are consistent with one Ru(II)-centered oxidation and three ligand-centered reductions. Photophysical behaviors are investigated by UV–Vis absorption and fluorescence spectrometry. The three complexes show metal-to-ligand charge transfer absorption at 445–453 nm and emission at 571–593 nm.
Keywords: Ru(II) complex; Dibenzo-18-crown-6; UV–Vis absorption; Electrochemistry; Emission;

A new organomercury(II) compound derived from both 3-ferrocenyl-2-crotonic acid and its decarboxylation product by Zifeng Li; Gang Li; Lipeng Wang; Jingxia Wu; Zongpei Zhang (691-693).
A new organomercury(II) compound, [Hg(OOCCH=(CH3)CFc)(CH=(CH3)CFc)] · MeOH (Fc = (η 5-C5H5)Fe(η 5-C5H4)) (1) was obtained by the reaction of Hg(OAc)2 with FcC(CH3)=CHCOONa in methanol solution. X-ray structural analysis reveals that the center Hg(II) ion is two-coordinated by the FcC(CH3)=CHCOO unit and the decarboxylation FcC(CH3)=CHC unit. Its thermal properties were investigated.A new Hg(II) complex [Hg(OOCCH=(CH3)CFc)(CH=(CH3)CFc)] · MeOH (Fc = (η 5-C5H5)Fe(η 5-C5H4)) (1) was obtained by the reaction of Hg(OAc)2 with FcC(CH3)=CHCOONa in methanol solution. X-ray structural analysis reveals that the center Hg(II) ion is two-coordinated by the FcC(CH3)=CHCOO unit and the decarboxylation FcC(CH3)=CHC unit. This is the first example of Hg(II) monomer containing both ferrocenyl carboxylate and its decarboxylation product. Its thermal properties were investigated under N2.
Keywords: Organomercury(II); Crystal structure; Decarboxylation; Ferrocene-substituted carboxylate; Thermal properties;

A simple and efficient one-pot synthetic methodology for the preparation of 1,1′-ferrocenediylbis-(methyltriphenylphosphonium iodide) is described. And the obtained salt has been used for the construction of ferrocene-containing pyridine ligands 3a–b. Electrochemical investigations of 3a–b have demonstrated that upon addition of Hg2+ and Zn2+ results in large shifts of respective Fc/Fc+ redox couple to more positive potentials. Titration experiment shows that the current associated with the new redox couple increases linearly with the concentration of Hg2+ until a full equivalent has been added, which suggests that 3b is a good candidate for an amperometric sensor to detect the toxic Hg2+.A simple and efficient one-pot synthetic methodology for the preparation of 1,1′-ferrocenediylbis-(methyltriphenylphosphonium iodide) is described. And the obtained salt has been used for the construction of ferrocene-containing pyridine ligands 3a–b. Electrochemical investigations of 3a–b have demonstrated that upon addition of Hg2+ and Zn2+ results in large shifts of respective Fc/Fc+ redox couple to more positive potentials. Titration experiment shows that the current associated with the new redox couple increases linearly with the concentration of Hg2+ until a full equivalent has been added, which suggests that 3b is a good candidate for an amperometric sensor to detect the toxic Hg2+.
Keywords: Phosphonium iodide; Wittig reaction; Electrochemical sensors;

Formation and luminescence of 1D helical polymeric excimer from Pt-MeO-salen precursor by Wen-Li Chai; Wen-Juan Jin; Xing-Qiang Lü; Wei-Yu Bi; Ji-Rong Song; Wai-Kwok Wong; Feng Bao (699-702).
With the amorphous Pt-MeO-salen solid (MeO-salen =  N,N′-bis(3-methoxy-salicylidene)-ethylene-1,2-diamine) as the precursor, a new 1D polymeric complex [K2(Pt-MeO-salen)2Ni(CN)4] n  · 0.5nEt2O (1) has been characterized. The luminescent property of the complex shows that the 1D helical stacking of well-defined Pt-MeO-salen monomers has modulated the energy order of the excited state in solid state at different temperatures.With the amorphous Pt-MeO-salen solid (MeO-salen =  N,N′-bis(3-methoxy-salicylidene)-ethylene-1,2-diamine) as the precursor, a new 1D polymeric complex [K2(Pt-MeO-salen)2Ni(CN)4] n  · 0.5nEt2O (1) has been characterized. The luminescent property of the complex shows that the 1D helical stacking of well-defined Pt-MeO-salen monomers has modulated the energy order of the excited state in solid state at different temperatures.
Keywords: Self-assembly; Excimer; Phosphorescence; Platinum(II); MeO-salen Schiff-base;

Two new complexes, [Cu(L)2(CH3COO)2(H2O)] · 6H2O (1) and [Cu2(L)2(CH3COO)4] · 2C2H5OH (2) (where L= N-(4-chlorophenyl)-3-pyridinecarboxamide), have been synthesized. Solvents control the coordination mode to form different supramolecular assemblies. Complexes 1 and 2 represent 3D and 2D networks, respectively. Interestingly, two scarcely reported cyclic water tetramers with C2h and D2h symmetries simultaneously populated in the channels of 1 have been observed.Two new complexes, [Cu(L)2(CH3COO)2(H2O)] · 6H2O (1) and [Cu2(L)2(CH3COO)4] · 2C2H5OH (2) (where L= N-(4-chlorophenyl)-3-pyridinecarboxamide), have been synthesized by altering the solvent of reaction system. For 1, the mononuclear complex is extended into a 3D supramolecular architecture through intricate non-covalent interactions. Unexpectedly, two scarcely reported cyclic water tetramers with C2h and D2h symmetries simultaneously exist in a 1D water chain. Whereas the dinuclear complex 2 represents a 2D framework by double hydrogen bonds with solvent ethanol molecules and π–π stacking interactions. In addition, the luminescent properties of them are also discussed.
Keywords: Solvent-induced assembly; Crystal structure; Supramolecular; Water cluster;

In situ solvothermal rearrangement and deamination of 3,6-di(2-pyrazinyl)-1,4-dihydro-1,2,4,5-tetrazine (bpztzH2) has been applied to generate two new photoluminescent d10 coordination polymers with carboxylates and 2-(5-(pyrazin-2-yl)-1H-1,2,4-triazol-3-yl)pyrazine (bpztzH2).Hydrothermal reaction of Cd(OAc)2  · 4H2O with 3,6-di(2-pyrazinyl)-1,4-dihydro-1,2,4,5-tetrazine (dpztzH2) at 165 °C resulted in the formation of a one-dimensional (1D) coordination polymer [Cd3(OAc)3(dpzt)3] · 2H2O (1) (dpztH = 2-(5-(pyrazin-2-yl)-1H-1,2,4-triazol-3-yl)pyrazine) and a new 3D microporous coordination network [Cd2(2,4,6-pyta)(dpzt)(H2O)] · 2H2O (2) when pyridine-2,4,6-tricarboxylic acid (2,4,6-pytaH3) ligand was employed in the above reaction system, in which the anionic dpzt ligand was resulted from the in situ solvothermal rearrangement and deamination of dpztzH2. Both complexes emit strong photoluminescence.
Keywords: Cadmium; Hydrothermal reaction; Coordination polymer; Photoluminescence; 2-(5-(Pyrazin-2-yl)-1H-1,2,4-triazol-3-yl)pyrazine;