Inorganic Chemistry Communications (v.9, #1)

Contents List (iii-xi).

The anhydrous CeX3 solids with X = Cl, Br, I show two emission bands which are separated by ca. 2000 cm−1 due to spin–orbit coupling. The longer-wavelength maximum appears at λ max  = 362 nm for CeCl3, 390 nm for CeBr3 and 514 nm for CeI3. It is suggested that this red shift is caused by an increasing interaction of the cerium 5d orbitals with the halide nd orbitals. Accordingly, the emission originates from a metal-centered 4f 5d excited state which is mixed with a cerium 4f → halide nd MLCT state.Qualitative MO scheme for CeIII halide complexes including the lowest-energy transition in absorption (A) and emission (E)The anhydrous CeX3 solids with X = Cl, Br, I show two emission bands which are separated by ca. 2000 cm−1 due to spin–orbit coupling. The longer-wavelength maximum appears at λ max  = 362 nm for CeCl3, 390 nm for CeBr3 and 514 nm for CeI3. It is suggested that this red shift is caused by an increasing interaction of the cerium 5d orbitals with the halide nd orbitals. Accordingly, the emission originates from a metal-centered 4f 5d excited state which is mixed with a cerium 4f → halide nd MLCT state.
Keywords: Electronic spectra; MLCT; Luminescence; Cerium; Halides;

Synthesis and crystal structure of octa(ε-caprolactam)neodymium(III) hexa(isothiocyanate)chromate(III) by E.V. Cherkasova; A.V. Virovets; E.V. Peresypkina; N.V. Podberezskaya; T.G. Cherkasova (4-6).
Ionic complex prepared from NdCl3, ε-caprolactam and K3[Cr(NCS)6] in water solution and structurally characterized.The novel mixed-ligand ionic complex compound [Nd(ε-caprolactam)8][Cr(NCS)6] was prepared by the reaction between NdCl3, ε-caprolactam and K3[Cr(NCS)6] in water solution and structurally characterized. Crystals are triclinic, space group P 1 ¯ , a  = 14.2438(6) AA, b  = 14.5641(6) Å, c  = 17.0308(7) Å, α  = 92.5180(10)°, β  = 91.0130(10)°, γ  = 108.6020(10)°, V  = 3343.3(2) Å3, Z  = 2, T  = 90 K, D x  = 1.440 g cm−3, R  = 0.0342 for 16,296 (I  > 2σI). Caprolactam ligands are completely ordered. The neodymium(III) atom is in distorted square-antiprismatic environment of eight oxygen atoms of L ligands, Nd–O = 2.37–2.54 Å. NH groups of caprolactam ligands are involved in hydrogen bonding forming NH…O intramolecular and NH…S(CN) inter-ionic contacts so that each cation is joined to three anions and vice versa.
Keywords: ε-Caprolactam; Neodimium; Isothiocyanate; Chromium; Crystal structure;

Nitrocellulose templated hierarchical pore structure in mesoporous thin films by X. Shari Li; Glen E. Fryxell; Chongmin Wang; James Young (7-9).
A novel and simple method for templating hiearchical pore structure in mesoporous ceramic oxide thin films is described.A novel and simple method for templating hiearchical pore structure in mesoporous ceramic oxide thin films is described.
Keywords: Mesoporous; Nanopore; Templated synthesis; Thin films; Cellulose nitrate; Nitrocellulose;

The oxidation of styrene with molecular oxygen at 25 °C under normal atmospheric pressure of O2 occurs efficiently in the presence of Schiff base Mn(III) complexes bearing two aza crown ether pendant. Crown ether effect on the catalytic oxidation of styrene is discussed, and the alkali metal ions and alkali earth metal ions added into the oxidation system can accelerate the conversion of styrene into benzaldehyde.The oxidation of styrene with molecular oxygen at 25 °C under normal atmospheric pressure of O2 occurs efficiently in the presence of Schiff base Mn(III) complexes bearing aza crown ether pendant. Crown ether effect on the catalytic oxidation of styrene is discussed, and the alkali metal ions and alkali earth metal ions added into the oxidation system can accelerate the conversion of styrene into benzaldehyde.
Keywords: Aza crown ether; Catalytic oxidation; Styrene; Schiff base Mn(III) complexes; Molecular oxygen;

The reactivity of Al(III) towards 2-(4,5-dihydro-1,3-oxazol-2-yl)phenol and 2-(4,5-dihydro-1,3-imidazol-2-yl)phenol is reported. The coordination ability, the stoichiometry, and the stability of the adducts formed in solution were studied by UV–Vis spectroscopy and by fluorescence. The efficiency of selectively detecting Al(III) for the two molecules is presented.Coordination ability of Al(III) towards 2-(4,5-dihydro-1,3-oxazol-2-yl)phenol (1) and 2-(4,5-dihydro-1,3-imidazol-2-yl)phenol (2) was studied added to the determination of the stoichiometry of the adducts formed in solution. The fluorogenic sensor character, that means efficiency and selectivity, of the two studied molecules was then quantified.
Keywords: Aluminium; Detection; Fluorescence; Oxazoline; Imidazoline;

Formation of polar crystals of a chiral dinuclear nickel(II) complex and their pyroelectric effect and electro-optic effect by Hiroshi Sakiyama; Mikio Yamasaki; Tetsuya Suzuki; Yoshio Watanabe; Rie Ito; Akimasa Ohnishi; Yuzo Nishida (18-20).
Polar crystals were formed using a chiral dinuclear nickel(II) complex as a building unit. The crystals showed pyroelectric and second-order electro-optic effects.Polar crystals were formed using a chiral dinuclear nickel(II) complex [Ni2(bomp)(R/S-OCOCH(CH3)Ph)2]BPh4 as a building unit. [H(bomp): 2,6-bis[bis(2-methoxyethyl)aminomethyl]-4-methylphenol; H(R/S-OCOCH(CH3)Ph): R/S-2-phenylpropionic acid]. Single-crystal X-ray analysis revealed that the symmetry of the crystal was C2 and the complex cations were orientated along the polar axis. The crystals showed pyroelectric and second-order electro-optic effects, which are characteristic of polar materials.
Keywords: Polar crystal; Chiral dinuclear nickel(II) complex; Pyroelectric effect; Electro-optic effect;

Three kinds of new nickel(II) complexes of α-isoxazolylazo-β-diketones with blue-violet light absorption were synthesized. It is found that these nickel(II) complexes had potential application for high density digital versatile disc-recordable (HD-DVD-R) system due to their good solubility in organic solvents, reasonable and controllable absorption spectra, high thermal stability and high reflectivity contrast (>50%).Three kinds of new nickel(II) complexes of α-isoxazolylazo-β-diketones with blue-violet light absorption were synthesized. Their structures were postulated based on elemental analysis, MS and FT-IR spectra. Smooth films on K9 glass substrates were prepared using the spin-coating method. The absorption properties and thermal stability of these complexes were discussed. The static optical recording test for high density digital versatile disc-recordable (HD-DVD-R) system was also studied.
Keywords: Nickel(II) complexes; α-Isoxazolylazo-β-diketones; Spin-coating film; Absorption spectra; Thermal stability; HD-DVD-R;

A neutral framework composite containing arrays of {V4O12} motifs covalently linked through {Co(C13H14N2)2} units has been synthesized and characterized. The new material is an attractive model system for studying the structures of metallo-organic biomolecules in living organisms by using solid state NMR spectroscopy.Hydrothermal reaction of NH4VO3, CoSO4  · 7H2O, 4,4′-trimethylenedipyridine (4,4′-tmdp = C13H14N2), and H2O yielded a new hybrid species, [{Co2(C13H14N2)4}V4O12], containing arrays of {V4O12} rings covalently linked through metal-organic units, {Co(C13H14N2)2}, into a three-dimensional open-framework structure. The novel material has been characterized by single crystal X-ray diffraction, infrared spectroscopy, elemental analysis, thermogravimetric analysis, and magnetic susceptibility measurement. The new material is potentially an attractive model compound for studying the structures of metallo-organic biomolecules by solid state NMR spectroscopy.
Keywords: Hybrid material; Hydrothermal synthesis; Crystal structure; Framework structure; Solid-state NMR model compound;

A novel selenium–molybdenum oxide chain inserted with copper (II) complex: Synthesis, structure, and magnetic property by Wenju Wang; Lin Xu; Guanggang Gao; Wenjia An; Yunfeng Qiu; Zhenqing Wang (29-33).
A one-dimensional polyoxomolybdate compound inserted with both selenite and copper (II) complex, [(CuO3bipy)2(SeO3)2(Mo6O18)] (bipy = 2,2’-bipyridine), has been hydrothermally synthesized and structurally characterized. This is the first example of polyoxomolybdate framework modified by both selenite and transition metal complex.A one-dimensional polyoxomolybdate compound inserted with both selenite and copper (II) complex, [(bipy)CuSeMo3O12] n , has been hydrothermally synthesized and structurally characterized. This is the first example that polyoxomolybdate framework modified by both selenite and transition metal complex. A strong ferromagnetic interaction occurred in this compound due to magnetic coupling between copper (II) centers.
Keywords: Hydrothermal synthesis; Polyoxomolybdate; Copper (II) complex; Selenium; Magnetic property;

A pentanuclear oxovanadium(V) phosphate complex with phenanthroline by Luís Mafra; Filipe A. Almeida Paz; Fa-Nian Shi; Christian Fernandez; Tito Trindade; Jacek Klinowski; João Rocha (34-38).
A novel crystalline organic–inorganic hybrid oxovanadium(V) phosphate complex, {[V2O4(Phen)2(PO4)]2VO(OH)}3/4 {[V2O4(Phen)2(HPO4)]2}1/4  · 4.5H2O (where Phen = 1,10-phenanthroline), was isolated and characterised structurally using several techniques, among which 51V and 31P solid-state NMR studies proved unequivocally the presence of two coordination environments for the V5+ centres.A novel crystalline organic–inorganic hybrid oxovanadium(V) phosphate complex, {[V2O4(Phen)2(PO4)]2VO(OH)}3/4 {[V2O4(Phen)2(HPO4)]2}1/4  · 4.5H2O (where Phen = 1,10-phenanthroline), was isolated using the hydrothermal synthetic approach, and characterised structurally using thermal (TG and DSC) and CHN elemental analysis, vibrational spectroscopy (IR and Raman), single crystal X-ray diffraction and solid-state NMR. The structure contains two similar binuclear dioxovanadium(V) moieties, with all V5+ centres in a highly distorted octahedral coordination geometry. These are further bridged via a fifth V5+ centre, in a highly distorted tetrahedral coordination geometry, leading to the formation of a pentanuclear moiety. Individual complexes close-pack in the solid-state via offset π–π (between neighbouring phenanthroline residues) and hydrogen bonding interactions (with the water molecules of crystallisation). 51V and 31P solid-state NMR proved unequivocally the presence of these two coordination environments for the V5+ centres.
Keywords: Oxovanadium phosphate; Organic–inorganic hybrid; Hydrothermal synthesis; 51V; 31P; Solid-state NMR; Crystal structure;

Photolysis of Mo(CO)(NO)(DPPE)(S2CNEt2) and [Mo(CO)3(NO)(DPPE)]PF6 in frozen matrices results in the isomerization of a linear nitrosyl ligand to its side-on, η2-NO isomer. These results are discussed in the context of recent studies by Kunkely and Vogler [H. Kunkely, A. Vogler, Inorg. Chem. Commun. 7 (2004) 767–769] describing nitrosyl loss during solution photolysis of an analogous dimethyldithiocarbamate derivative.Photolysis of Mo(CO)(NO)(DPPE)(S2CNEt2) and [Mo(CO)3(NO)(DPPE)]PF6 in frozen matrices results in the isomerization of a linear nitrosyl ligand to its side-on, η2-NO isomer. These results are discussed in the context of recent studies by Kunkely and Vogler [H. Kunkely, A. Vogler, Inorg. Chem. Commun. 7 (2004) 767–769] describing nitrosyl loss during solution photolysis of an analogous dimethyldithiocarbamate derivative.
Keywords: Nitrosyl linkage isomer; Photochemistry; Molybdenum;

Two new polymeric Cu sulfates with 4,4′-bipyridine have been isolated and structurally characterized. Cu(I) compound exhibit chain structure. Cu(II) polymer consists of 2D interwoven networks that are stacked together by hydrogen bonding.Two new composite inorganic–organic materials from the copper/sulfate/4,4′-bipyridine family have been isolated and structurally characterized. The structure of the monovalent compound exhibits double chains in which the two parallel –Cu–bipy– chains are interconnected through sulfate bridges. The divalent polymer consists of two-dimensional interwoven networks that are stacked together by hydrogen bonding between the layers.
Keywords: Copper complex; Coordination polymer; Sulfate coordination; Bipyridine; Solvothermal synthesis;

A dihydroxo-bridged dichromium(III) complex with pmida (N-(2-pyridylmethyl)iminodiacetate), consisting of a three-dimensional network in which [Cr2(μ-OH)2(pmida)2] units are alternatively linked by hexacyclic hydrogen-bonded rings adopting the chair conformation, has been synthesized and characterized structurally and magnetically.A dihydroxo-bridged dichromium(III) complex, [Cr2(μ-OH)2(pmida)2] · 4H2O (pmida =  N-(2-pyridylmethyl)iminodiacetate), has been prepared and characterized structurally and magnetically. The complex consists of a three-dimensional network in which [Cr2(μ-OH)2(pmida)2] units are alternatively linked by hexacyclic hydrogen-bonded rings adopting the chair conformation. The magnetic susceptibility measured over the range 3–300 K shows there is the antiferromagnetic interaction between the two chromium(III) ions. Based on the Hamiltonian written as H ^ = - 2 JS 1 S 2 , best fitting for the experimental data leads to J  = −13.0 cm−1.
Keywords: Chromium(III); N-(2-Pyridylmethyl)iminodiacetate; Crystal structure; Magnetic property;

Synthesis of new self-assembled octahedrons containing group 14 elements dative bonding of pyrimidine derivatives with palladium ions by Yoshiyuki Miura; Kanako Ito; Seigo Ohta; Keiko Yano; Masato Nanjo; Yoko Usui; Kunio Mochida (50-52).
Self-assembly reactions of di{4-(5-pyrimidyl)phenyl}dimethyl-silane and -germane with (ethylenediamine)palladium dinitrate led to the formation of new group 14 elements (Si Ge)-containing octahedral supramolecules.Self-assembly reactions of di{4-(5-pyrimidyl)phenyl}dimethylsilane and -germane with (ethylenediamine)palladium dinitrate in ratio of 1:2 led to the formation of new octahedral supramolecules containing group 14 elements (Si,Ge), respectively. The structure of the silicon-bridged octahedron was fully identified by spectroscopic methods coupled with X-ray diffraction analysis.
Keywords: Supramolecule; Octahedron; Pyrimidine derivatives; Heavier carbon homologues; X-ray diffraction;

Mono- and di-nuclear platinum(II) complexes containing O- and N-bonded acetamide by Erin J. Ziolkowski; Peter Turner; Louis M. Rendina (53-56).
The preparation, characterization, and interconversion reactions of a series of novel O- and N-bonded acetamide and deprotonated N- and N,O-bonded acetamido derivatives of platinum(II)-terpy (terpy = 2,2′:6′,2″-terpyridine) are described. The X-ray structures of the mononuclear N-acetamido and an unusual dinuclear N,O-acetamido species are also reported.The preparation, characterization, and interconversion reactions of a series of novel O- and N-bonded acetamide and deprotonated N- and N,O-bonded acetamido derivatives of platinum(II)-terpy (terpy = 2,2′:6′,2″-terpyridine) are described. The X-ray structures of the mononuclear N-acetamido and an unusual di-nuclear N,O-acetamido species are also reported.
Keywords: Platinum(II) complex; Acetamide; Linkage isomers; X-ray structures;

The solvothermal treatment of cobalt/zinc salt, ethylenediamine and dicarboxylate in acetonitrile produced two one-dimensional coordination polymers with methylimidazoline ligand formed by cycloadditon reaction of ethylenediamine and acetonitrile.The solvothermal treatment of cobalt nitrate (or zinc acetate), ethylenediamine and dicarboxylate in acetonitrile produced two one-dimensional coordination polymers [Co(mimz)2(ox)] n (1) and [Zn(mimz)2(ip)] n (2) (mimz  =  2-methylimidazoline, ox = oxalate, ip = isophthalate) which ligand involving in situ formation of imidazoline ligand by cycloaddition reaction of ethylenediamine and acetonitrile.
Keywords: Imidazoline; Ligand reaction;

A novel Ag6 cluster with S6 symmetry, [Ag(pfbt)(PPh3)]6 1 (Hpfbt = pentafluorobenzenethiol), was prepared by a reaction of the insoluble precursor [Ag(pfbt)] 2 and PPh3. Water-soluble silver(I) carboxylate [Ag(Hpyrrld)]2 was used for preparation of 2.A nanoscale drum-like hexanuclear silver(I) cluster [Ag(pfbt)(PPh3)]6 1 (Hpfbt = pentafluorobenzenethiol), which showed the arrays of channels based on its self-assembly in the solid, was obtained by the 1:1 molar-ratio reaction of the insoluble polymeric precursor [Ag(pfbt)] 2 and PPh3 in chloroform. Synthetic yield and purity of 1 were strongly dependent on the purity of 2. Compound 2 with higher purity was prepared in good yield using light-stable and water-soluble silver(I) carboxylate [Ag(Hpyrrld)]2 (H2pyrrld = 2-pyrrolidone-5-carboxylic acid) as the silver(I) source.
Keywords: Nanoscale hexanuclear silver(I) cluster; Solid channel structure; Pentafluorobenzenethiol; Triphenylphosphine; 2-Pyrrolidone-5-carboxylic acid;

Synthesis, structure and magnetic properties of a tin cobalt phosphate framework, SnCo2(H2O)2(PO4)2  · H2O by Tolulope O. Salami; Xiaojuan Fan; Peter Y. Zavalij; Scott R.J. Oliver (64-67).
A three-dimensional mixed-metal phosphate was obtained by hydrothermal methods. Layers of corner- and edge-sharing cobalt octahedra are capped by phosphate groups, which in turn bond to interlayer Sn centres to define the framework. The material contains unidimensional channels and its magnetic and thermal properties are discussed.The hydrothermal inorganic reaction of cobalt chloride, tin oxalate and phosphoric acid yields a three-dimensional metal phosphate structure containing cobaltate layers. Hydrated tin phosphate chains connect the layers, defining unidimensional channels that contain occluded water molecules. Thermal and magnetic behaviour are also discussed. A cusp around 3.5 K and a negative Curie temperature of −35.9 K indicate antiferromagnetic exchange interactions between the Co(II) centers in the solid. The magnetic behavior follows the Curie–Weiss law in the 25–300 K range, with an effective magnetic moment of 3.18  μ B.
Keywords: Tin cobalt phosphate; Mixed-metal phosphate; Three-dimensional framework; Hydrothermal synthesis; Magnetic measurements;

Substituting the 2-thenyloxy or 3-thenyloxy group at the 4′-position of the terpyridine ligand induces new interesting physicochemical properties of the corresponding ruthenium complexes. Particularly, the O–CH2 spacer prevents the conjugation between the Π* ligand orbitals.Two ligands whose general formula is R-terpy with terpy = 2,2′:6′,2″-terpyridine bearing at the 4′-position a substituent R = 2-thenyloxy and 3-thenyloxy were synthesised. The electronic spectra and the electrochemical behaviour of the corresponding Ru(II) complexes were investigated. The donor effect of the grafted groups as the non-conjugation between the Π* ligand orbitals of the terpyridine and the thienyl groups induce an increase of the energy level of the LUMO.
Keywords: Ruthenium complexes; 2,2′:6′,2″-Terpyridine; Thenyloxy-2,2′:6′,2″-terpyridine; Electropolymerisation;

A new binuclear complex, {[Cu(μ-PhPPy2)(CH3CN)]ClO4}2 (1), is synthesized by a reaction of [Cu(CH3CN)4]ClO4 with PhPPy2. Dimeric unit, [ Cu ( μ - PhPPy 2 ) ( CH 3 CN ) ] 2 2 + , can be utilized as building block precursor to construct coordination polymer [Cu2(μ-PhPPy2)2(μ-SO4)] (2) by replacement of coordinated acetonitrile molecules in 1 with bridging ligand ( SO 4 2 - ) . Both 1 and 2 exhibit strong green emissions in solid state at room temperature.A new binuclear complex, {[Cu(μ-PhPPy2)(CH3CN)]ClO4}2 (1) is synthesized by a direct reaction of [Cu(CH3CN)4]ClO4 with PhPPy2. Dimeric cation of 1, [ Cu ( μ - PhPPy 2 ) ( CH 3 CN ) ] 2 2 + , can be utilized as building block precursor to construct coordination polymer [Cu2(μ-PhPPy2)2(μ-SO4)] (2) by replacement of coordinated acetonitrile molecules with bridging ligand ( SO 4 2 - ) . Both 1 and 2 exhibit strong green emissions in solid state at room temperature. Crystal structures of 1 and 2 have been determined by single crystal X-ray diffraction.
Keywords: Binuclear copper(I) complex; Polymer; Bis(2-pyridyl)phenylphosphine; Luminescence;

S2O x macrocyclic ligands with (L 1: x  = 3 and L 2: x  = 4) and without (L 3: x  = 3 and L 4: x  = 4) dibenzo-subunit were employed as extractants. All of the ligands shows silver(I) selectivity and the silver picrate was more extractable with L 1 and L 2 when compared with L 3 and L 4. The enhanced extractability for the silver picrate by L 1 and L 2 was revealed due to the additional stabilization of the complexes, [Ag(L)picrate], by anion–ligand π–π interaction between the picrate ion and one benzo-subunit in the ligand.S2O x macrocyclic ligands with (L 1: x  = 3 and L 2: x  = 4) and without (L 3: x  = 3 and L 4: x  = 4) dibenzo-subunit were employed as extractants to clarify the anion–ligand interaction on the extraction efficiency of soft metal picrates. All of the ligands shows silver(I) selectivity and the silver picrate was more extractable with L 1 and L 2 when compared with L 3 and L 4. From the X-ray and NMR data, the enhanced extractability for the silver picrate by L 1 and L 2 was revealed due to the additional stabilization of the complexes, [Ag(L)picrate], by anion–ligand π–π interaction between the picrate ion and one benzo-subunit in the ligand. Such anion–ligand interaction would give a valuable hint for the molecular design of new extractants for the soft metal ions including silver(I).
Keywords: Thiaoxa macrocycles; Solvent extraction; Anion–ligand π-stacking interaction; Picrate effect; Crystal structure; NMR;

Reactions of [MOS3]2− (M = Mo, W) with 3 equiv. of CuS2P(OMe)2 led to the formation of two novel polymeric clusters [Et4N][MOS3Cu3{S2P(OMe)2}2] (1, M = Mo; 2, M = W). Complexes 1 and 2 are the first examples which contain anionic 2D (6,3) net constructed by nest-shaped [MOS3Cu3  · S2P(OMe)2] cluster units and polydentate [S2P(OMe)2] ligands. Complex 1 shows good second-order NLO performance.Reactions of thiomolybdate or thiotungstate [MOS3]2− (M = Mo, W) with 3 equiv. of CuS2P(OMe)2 led to the formation of two novel Mo(W)/Cu/S polymers [Et4N][MOS3Cu3{S2P(OMe)2}2] (1, M = Mo; 2, M = W). Single-crystal X-ray diffraction studies reveal that 1 and 2 are the first examples that containing anionic 2D (6,3) net with nest-shaped [MOS3Cu3  · S2P(OMe)2] clusters as 3-connecting nodes and tridentate [S2P(OMe)2] ligands as linkers. Both 1 and 2 crystallize in a noncentrosymmetric space group and the former polymer shows good second-order NLO performance.
Keywords: Thiotungstate; Thiomolybdate; 2D layer structure; Mo(W)/Cu/S polymers; Crystal structure; Second-order NLO material;

First ferrocenylstibines and their molecular structures by Pankaj Sharma; Jose G. Lopez; Carmen Ortega; Noe Rosas; Armando Cabrera; Cecilio Alvarez; Alfredo Toscano; Elizabeth Reyes (82-85).
First report on ferrocenylstibines Ph2SbFc containing the pendant arm [2-(Me2NCHR)] [where R = H (1) or Me (2)] on ferrocenyl ring were synthesized, and reaction of (1) with CH3I was carried out to obtain the monoammonium salt {[2-(Me3N+CH2)Fc]}SbPh2[I]. Heterobimetallic stibine (1) does not show intramolecular Sb–N interactions while the stibine (2) is stabilized by intramolecular Sb–N interactions.Stibines Ph2SbFc containing the pendant arm [2-(Me2NCHR)] [where R = H(1) or Me(2)] on ferrocenyl ring were synthesized, and reaction of (1) with CH3I was carried out to obtain the monoammonium salt {[2-(Me3N+CH2)Fc]} SbPh2[I]. All new stibines have been characterized by various physicochemical techniques. The structures of all these 1,2-disubstituted ferrocenylstibines were determined by X-ray diffraction analyses. This is the first report on the stibines containing disubstituted ferrocenyl group and it is worth mentioning that even monosubstituted ferrocenylstibines are virtually unknown. Heterobimetallic stibine (1) does not show intramolecular Sb–N interactions while the stibine (2) is stabilized by intramolecular Sb–N interactions.
Keywords: Ferrocene; Stibines; Hypervalent; Heterobimetallic; X-ray structure;

One-dimensional copper polymers with pentadentate diazine ligands by Yan Bai; Dongbin Dang; Xin Cao; Chunying Duan; Qingjin Meng (86-89).
Two new one dimensional copper(II) polymers based on tetranuclear units was achieved via self-assembly from N3O2 pentadentate ligand and structurally characterized.One-dimensional copper(II) polymers [(Cu4L2)(NO3)4] n (1) and [(Cu4L2)Cl4] n (2) (H2L = salicylaldehyde-2-pyridinecarboxyl-hydrazone) were achieved via self-assembly. The Cu⋯Cu separations were ca. 2.90 and 4.75 Å for the phenoxide oxygen bridged pair and the N–N bridged pair with antiferromagnetic spin exchanges between Cu(II) ions.
Keywords: Copper(II) complex; One-dimensional polymer; Crystal structure; Magnetic property;

A new ligand for the formation of a 3D structure by significant C–H⋯S hydrogen bonds and π–π interactions by Hong-Ping Zhou; Yong-Min Zhu; Jing-Jin Chen; Zhang-Jun Hu; Jie-Ying Wu; Yi Xie; Min-Hua Jiang; Xu-Tang Tao; Yu-Peng Tian (90-92).
Two-dimensional grid structure of 1 contains cavity, single crystal X-ray analysis has revealed that the 3D framework of the title compound is formed by significant C–H⋯S hydrogen bonds and π–π interactions. The solid-state fluorescent determinations show that the complex exhibits a strong emission band at 403 nm.A novel 3D coordination polymer, [Cd(diec)2(NCS)2] n (1) (diec = 3,6-diimidazolyl-9-ethylcarbazole) has been prepared by reacting Cd(SCN)2 with the diec ligand. Single crystal X-ray analysis has revealed that the 3D framework of the title compound is formed by significant C–H⋯S hydrogen bonds and π–π interactions. The solid-state fluorescent determinations show that the complex exhibits a strong emission band at 403 nm.
Keywords: 3D coordination polymer; Crystal structure; Hydrogen bonds;

Synthesis and characterization of cyclopalladated ionic complexes by Teresa Pugliese; Nicolas Godbert; Iolinda Aiello; Mauro Ghedini; Massimo La Deda (93-95).
Ionic coordination compounds can be interesting molecular materials featuring ionic conductivity in solid thin films. Two series of new cyclopalladated [(CN)Pd(NN)]CF3SO3 complexes, 1 and 2, are described.A series of new cationic ortho-metalated Pd(II) complexes of general formula [(CN)Pd(NN)]X (HCN = 2-phenylpyridine, H(PhPy) or benzo[h]quinoline, H(BhQ); NN = ethylenediamine, 2,2′-bipyridine, 1,10-phenanthroline, N,N,N′,N′-tetramethylethylenediamine, 4,4′-dimethyl-2,2′-bipyridine, 4,7-dimethyl-1,10-phenanthroline, or 4,4′-dinonyl-2,2′-bipyridine; X = CF3SO3) are reported. Photophysical characterization of these species indicates that electronic transitions are prominently cyclometalating ligand-localized in character and nearly unaffected by the polarity of solvent in which the spectra are recorded.
Keywords: Ionic palladium complexes; Cyclometalation; Bis-chelated complexes;

Two unprecedented types of ligands with C2 symmetry, with comparable essential features, are proposed as supports for metal centres in bimetallic promotion of organic syntheses. Preparation and characterization of bis-chelating bipyridine ligands A and X-ray analysis of a related palladium binuclear complex are described. Synthesis and characterization of a dialdehyde intermediate for type B ligands are also reported.The binding chemistry of heavy metal cations to a thiolated nanoporous solid-phase sorbent is correlated with the Misono softness parameter, allowing for useful prediction of binding capacity.
Keywords: Sorbent; Monolayer; Misono; Heavy metal; Thiol; Mercaptan; Sequestration; Binding capacity;

High and selective Ag(I) bulk liquid membrane transport with N,N-diethyl-N′-camphanyl thiourea and structure of the complex by Haile G. Berhe; Susan A. Bourne; Martin W. Bredenkamp; Catharine Esterhuysen; Michael M. Habtu; Klaus R. Koch; Robert C. Luckay (99-102).
The novel ligand N,N-diethyl-N′-camphanyl thiourea shows high and selective Ag(I) transport and extraction in the presence of Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II). A crystal structure shows monodentate and bidentate coordination modes to the metal ion.The novel N,N-diethyl-N′-camphanyl thiourea has been synthesised and characterised by conventional methods. It has been found by means of competitive three-phase transport and competitive two-phase extraction studies to show very high and selective Ag(I) transport and extraction in the presence of Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) using the pH gradient method. A crystal structure suggests that a complex Ag2[(HL-S)(L-μ-S,O)]2 exists, where both monodentate and bidentate modes of coordination are involved.
Keywords: Silver(I); Transport; Extraction; Bulk liquid membrane; Silver–ligand complex;

The 4-ring of (bipy)Zn2(HPO3)2 is transformed to a new compound, [Zn4(HPO3)4(2,2′-bipy)4] · 11H2O, that contains a cluster of four zinc atoms, Zn–O–Zn linkages, and stabilizes a chain of hydrogen bonded water molecules in the crystal lattice.An infinite chain of hydrogen bonded loops of 8 and 10 water molecules are stabilized by the neutral zinc phosphite cluster [Zn4(HPO3)4(2,2′-bipy)4] · 11H2O. The cluster is prepared either by direct synthesis or by transformation of a (2,2′-bipy)2Zn2(HPO3)2 4-ring.
Keywords: Hydrogen bonding; Water chains; Zinc phosphite; Bipyridine; Zinc cluster;

A novel tetranuclear silver(I) cluster, [Ag2(Himdc)(PPh3)2]2 1 (H3imdc = imidazole-4,5-dicarboxylic acid), was prepared by a reaction among the Ag–O bonding precursor [Ag(R-Hpyrrld)]2 (H2pyrrld = 2-pyrrolidone-5-carboxylic acid), PPh3 and H3imdc in an organic solvent. By a reaction using increased amounts of PPh3, the monomeric complex [Ag(H2imdc)(PPh3)2] 2, was also obtained.A novel tetranuclear silver(I) cluster, [Ag2(Himdc)(PPh3)2]2 1 (H3imdc = imidazole-4,5-dicarboxylic acid; ON) was obtained by a reaction of the Ag–O bonding precursor [Ag(R-Hpyrrld)]2 (H2pyrrld = 2-pyrrolidone-5-carboxylic acid), PPh3 and H3imdc. The mononuclear complex, [Ag(H2imdc)(PPh3)2] 2, was also formed by the reactions using increased amounts of PPh3. In the solid state, complex 1 was a “bivalve”-like Ag4 cluster, while complex 2 showed a supramolecular arrangement of the 4-coordinate AgP2(NO) unit via the intermolecular hydrogen bonding interaction.
Keywords: Tetranuclear silver(I) cluster; Imidazole-4,5-dicarboxylic acid; Triphenylphosphine; 2-Pyrrolidone-5-carboxylic acid;

Bifunctional transition metal complexes as nucleic acid photoprobes and photoreagents by Frédéric Pierard; Andrée Kirsch-De Mesmaeker (111-126).
Functionalization of photo-active transition metal complexes by nucleic acid targeting moieties or by DNA reactive species allows the fine tuned design of new DNA luminescent probes and light-triggered reactive agents. This mini-review highlights recent advances in the development of such bifunctional assemblies as molecular tools for the study of genetic material.Transition metal complexes that bind to DNA have been the focus of extensive research aimed at increasing the understanding of genetic information processing and at developing ways to interfere with these mechanisms. Beside the continuous development of “dark reacting” artificial metallonucleases and metal-based chemotherapeutics such as cisplatin, photo-active octahedral metal complexes have been successfully used as DNA luminescent probes and light-driven reactive agents during the last decades. A recent emerging trend to improve their potential as molecular tools for studies of the genetic material is the design of bifunctional assemblies where the photo-active metal center is tethered through a flexible linker to a nucleic acid recognition or reactive moiety. This mini-review highlights some recent progresses in developing such bifunctional complexes through derivatization strategies ranging from the design of dimeric complexes and chromophore-quencher systems to the development of biotin–metal complex conjugates for avidin-mediated detection of biomolecules.
Keywords: DNA photoprobes; DNA photoreagents; Rhenium(I); Ruthenium(II); Rhodium(III); Bis-intercalator; Chromophore-quencher; Biotin–avidin;