Inorganic Chemistry Communications (v.10, #2)

Contents List (iii-xi).

Macropolyhedral boron-containing cluster chemistry: The reaction of syn-B18H22 with SMe2 and I2 in monoglyme: Structure of [7-(SMe2)-syn-B18H20] by Tomáš Jelínek; Bohumir Grüner; Ivana Císařová; Bohumil Štíbr; John D. Kennedy (125-128).
In contrast to the ready addition of ligands to nido single-cluster B10H14 the addition of a ligand onto nido: nido double cluster B18H22 needs an oxidizing agent: thus deprotonation of syn-B18H22 followed by treatment with I2 and SMe2 gives [7-(SMe2)-syn-B18H20].The reaction of B10H14 with two-electron ligands L to give L2B10H12 is not mimicked by B18H22. Instead, an oxidizing agent is required to introduce a ligand onto the {B18} skeleton: thus deprotonation of syn-B18H22 in monoglyme followed by treatment with I2 and SMe2 gives [7-(SMe2)-syn-B18H20] (41%).
Keywords: Borane cluster; Macropolyhedral; Ligand addition; X-ray structure; Oxidative addition of ligand; Ligand-borane complex; Fused clusters;

A new 3-D asymmetric mixed valence copper-azido coordination polymer, [CuI  · CuII(N3)(pzc)2(H2O)] n 1, has been synthesized and characterized, and its magnetic properties studied. In this compound, the azide acts as rare asymmetric μ 1,1,3 mode. The azide ligands and the Cu(2) ions act as 3-connecting nodes, and the Cu(1) ions act as 4-connecting nodes. The overall net takes rare topology with the Schläfli symbol of (6.82)(6.82)(6.85).A new 3-D mixed valence copper-azido coordination polymer, [CuI  · CuII(N3)(pzc)2 (H2O)] n 1, has been synthesized and characterized, and its magnetic properties studied. In this compound, the azide acts as rare asymmetric μ 1,1,3 bridging mode. The azide ligands and the Cu(2) ions act as 3-connecting nodes, and the Cu(1) ions act as 4-connecting nodes. The overall net takes rare topology with the Schläfli symbol of (6.82)(6.82)(6.85).
Keywords: Copper(I/II); 2-pyrazinecarboxylate; Azide; Crystal structure; Magnetic study; Asymmetric mode; Topology;

New nitrosyl ruthenium complex [RuCl(NO)(dcype)(bipy)](PF6)2: Synthesis, electrochemistry, NMR and ESI-MS/MS studies by Gustavo Von Poelhsitz; André Luiz Bogado; Gezimar Donizetti de Souza; Edson Rodrigues-Filho; Alzir Azevedo Batista; Márcio Peres de Araujo (133-138).
A new P−P/N−N containing Ru−NO complex was synthesized from cis-[RuCl2(dcype)(bipy)]. The complex was characterized by NMR (31P, 1H and 15N), ESI-MS, elemental analysis and cyclic voltammetry.Reactivity of cis-[RuCl2(dcype)(bipy)] (dcype = 1,2-bis(dicyclohexylphosphino)ethane and bipy = 2,2′-bipyridine) with nitric oxide afforded the new dicationic complex [RuCl(NO)(dcype)(bipy)]2+. The complex isolated as PF 6 - salt was characterized by spectroscopical, electrochemical and ESI-MS/MS techniques as well as elemental analysis. Surprisingly the analysis of 31P{1H} and 15N{1H} NMR spectra of the [RuCl(15NO)(dcype)(bipy)]2+ complex reveal that the NO is in trans position to one of the P atom of dcype. The IR spectrum showed the presence of υ NO in 1889 cm−1 with is in agreement with the presence of NO+, but based on 31P{1H} NMR analysis the nitrosyl do not behave as a strong π-acceptor since little (or none) trans structural effect was observed on 31P chemical shift compared to the precursor cis-[RuCl2(dcype)(bipy)]. In the ESI-MS analysis, we just have detected the intact nitrosyl complex in CH2Cl2 solutions, but in MeOH solutions, the ion [M−NO]+ was detected, indicating the lability of M−NO bond. MS n spectra with variable collision energy indicate a fragmentation pathway with radical bi-cyclohexyl-phosphine and two cyclohexene losses.

A new cobalt(III) complex salt, [cis-Co(en)2(H2O)Cl](C6H5SO3)2, has been synthesized and characterized by single crystal X-ray structure determination. This is a first structural report of the cation [Co(en)2(H2O)Cl]2+ in cis-configuration. The cations and anions are associated in chains by strong NH⋯O hydrogen bonds. The crystal lattice is stabilized by extensive hydrogen bonding besides coulombic forces of attraction.A new cobalt(III) complex salt, [cis-Co(en)2(H2O)Cl](C6H5SO3)2  · H2O] (I) has been synthesized and characterized by single crystal X-ray structure determination and NMR spectroscopy. This is a first report of the cobalt(III) cation in cis-configuration. The crystal lattice of the complex salt is stabilized by electrostatic forces of attraction and hydrogen bonding interactions.
Keywords: Cobalt(III); Coordination chemistry; Benzenesulphonate; X-ray crystallography; IR spectroscopy; UV/visible spectroscopy;

Lanthanide molecular oxohydroxides: Synthesis and characterisation of [Y44-O)(μ-OEt)2(μ,η2-AAA)22-AAA)3]23-OH)43-OEt)2 (HAAA = allylacetatoacetate) by Liliane G. Hubert-Pfalzgraf; Lauren Cauro-Gamet; Anne Brethon; Stephane Daniele; Philippe Richard (143-147).
The reaction between Y(μ5-O)(-OiPr)13 and allylacetoacetate (1:5 stoichiometry) afforded an octanuclear centrosymmetric cluster Y84-O)23-OH)43-OEt)2 (μ-OEt)4(μ,η2-AAA)42-AAA)6 after ethanolysis and hydrolysis–polycondensation. A similar compound was obtained with 2-(methacryloyloxy)ethyl acetatoacetate homo and copolymerization reactions were evaluated for both compounds.The reaction between Y5O(OPri)13 and allylacetatoacetate or 2-(methacryloyloxy)ethyl acetatoacetate in 1:5 stoichiometry afforded octanuclear oxohydroxo species. Structural characterization was achieved for the allylacetatoacetate derivative homo and copolymerisation reactions with styrene were evaluated for doping of polystyrene. Hydoxo species, Y4(OH)2(AAA)10, where also obtained by reacting Y[N(SiMe3)]3 and HAAA.
Keywords: Yttrium; Alkoxides; X-ray structure; Polymerizable ligands;

The oxonium ions O ( Au I PPh 3 ) 3 + and O ( Hg II Cl ) 3 + are phosphorescent at r.t. and 77 K, respectively. It is suggested that these ions which are characterized by a rather flat trigonal pyramid in the ground state undergo a distortion to a steeper pyramid in their phosphorescent states. This structural change is caused by metal–metal bonding in the excited state.The oxonium ions O ( Au I PPh 3 ) 3 + and O ( Hg II Cl ) 3 + are phosphorescent at r.t. and 77 K, respectively. It is suggested that these ions which are characterized by a rather flat trigonal pyramid in the ground state undergo a distortion to a steeper pyramid in their phosphorescent states. This structural change is caused by metal–metal bonding in the excited state.
Keywords: Electronic spectra; Photoluminescence; Phosphorescence; Gold; Mercury; Oxonium;

The metal ion retention properties of P(AGA) were investigated through the LPR technique. Results show that the affinity of ligand groups by the metal ions depends strongly on the pH, and the ligand groups involved on complex formation should be amide and carboxylate groups. It was studied by FT-IR and Far-IR spectroscopy.A water-soluble polymer, poly(2-acrylamido glycolic acid) was obtained by radical polymerization and characterized by FT-IR, 1H NMR, and 13C NMR spectroscopy. The metal ion retention properties were investigated through the liquid-phase polymer based retention (LPR) technique at different pHs and filtration factor Z. The affinity of the ligand groups for the metal ions depends strongly on the pH. At lower pH, the retention is lower than 50%, which increased as the pH increased. At pH 5, the polymer showed a high affinity and selectivity for Pb(II), and at pH 7 the P(AGA) formed stable complexes with Cu(II), Co(II), Ni(II), Cd(II), and Pb(II). Of the three potential ligand groups, amide, hydroxyl, and carboxylate groups, the carboxylate groups form the more stable complexes with the metal ions.
Keywords: Water-soluble polymer; Metal ions; Polymer–metal complexes; Acrylamido glycolic acid; Liquid-phase polymer based retention;

Complexation-induced distortion of a naphthalene unit symmetrically-substituted by two (N,N,P) ligands by Wei Ren; Feng-Bo Xu; Hu Xu; Hai-Bin Song; Zheng-Zhi Zhang (155-158).
A novel polydentate phosphanyl-pyridyl ligand BPNNNa and its Group 11 chelating binuclear complexes 1 and 2 were prepared. The latter are non-emission and exhibit folding deformation of the naphthalene spacers, which may be attributable to charge transfer interaction between metal atoms and naphthalene unit as well as the possible steric stress of the ligand.Binuclear complexes [M2(μ-BPNNNa)] [ BF 4 - ]2 (M = CuI, 1; M = AgI, 2) were prepared by reaction of 1,5-bis [{6-(diphenylphosphanyl)-2-pyridylmethyl}n-propylamino methyl]naphthalene (BPNNNa) with M(CH3CN)4 BF4 in CH2Cl2 and were structurally characterized by single crystal X-ray diffraction studies. In complexes 1and 2, BPNNNa acts as a chelating ligand and two dppy (2-(diphenylphosphino) pyridine) units with two metal atoms are linked together in head-to-tail mode to form an eight-membered ring, which exhibits an eclipsed conformation. A significant feature in complexes 1 and 2 is the deformation of the flat naphthalene unit, in which the two aryl moieties make an angle of 10.3° (1) and 7.2° (2), respectively. A weak Ag⋯Ag interaction is present in the complex 2.
Keywords: Binuclear complexes; Phosphanyl-pyridine ligands; Naphthalene; Deformation;

Structural characterization of a layered double salt Mn3(OH)2(SO4)2(H2O)2  · K2SO4 by Jie-Hui Yu; Ling Ye; Hong Ding; Yan Chen; Qin Hou; Xiao Zhang; Ji-Qing Xu (159-162).
The title 2-D layered double salt Mn3(OH)2(SO4)2(H2O)2  · K2SO4 (1) is built up of the dimers of edge-sharing Mn(1) octahedral, extended by the apices of Mn(2) octahedral together with μ3 and μ4 SO4 groups. With free K+ ion as guest species, the 2-D sheets are further self-assembled into a 3-D supramolecular network with 1-D channels through the Ow-H ⋯ O hydrogen-bonded interactions.The title layered double salt Mn3(OH)2(SO4)2(H2O)2  · K2SO4 (1) was obtained from a simple hydrothermal reaction of CdSO4  · 8/3H2O, MnCl2  · 4H2O, α-aminopyridine (apy) and KI. X-ray analysis reveals that the two-dimensional (2-D) sheet of 1 is built up of the dimers of edge-sharing Mn(1) octahedral, extended by the apices of Mn(2) octahedral together with μ3 and μ4 SO4 groups. With free K+ ion as guest species, the 2-D sheets are further self-assembled into a 3-D supramolecular network with 1-D channels through the Ow-H ⋯ O hydrogen-bonded interactions. The magnetic property of 1 was investigated, and a classical behavior is observed with an antiferromagnetic order below 12.5 K.

A novel 2D framework containing M2L2 24-membered rings interconnected through secondary N–H⋯I bonds by Lin Li; Jia-Xiang Yang; Hong-Ping Zhou; Yu-Peng Tian; Xu-Tang Tao; Min-Hua Jiang (163-165).
A novel complex, Hg2I4L2 (L: 2,2′-(ethane-1,2-diylbis(oxy))dibenzenamine), containing a “dumb-bell” channel in a 2D framework has been prepared. Single crystal X-ray analysis has revealed that two metal atoms and two ligands L form a M2L2 24-membered ring with a metal–metal separation of 6.836 Å in the complex. The whole structure was stabilized by weak π–π interactions and the N–H⋯I bonds to form 2D network.A novel complex, Hg2I4L2 (L: 2,2′-(ethane-1,2-diylbis(oxy))dibenzenamine), containing a “dumb-bell” channel in a 2D framework has been prepared. Single crystal X-ray analysis has revealed that two metal atoms and two ligands L form a M2L2 24-membered ring with a metal–metal separation of 6.836 Å in the complex. The whole structure was stabilized by weak π–π interactions and the N–H⋯I bonds to form 2D network. The thermal decomposition of free ligand L and complex A were studied using TG/DTG/DTA techniques. The thermogram reveals that complex A undergoes two steps between 155 and 370 °C, while there is only a single endothermic step in the free ligand L.
Keywords: Supramolecular chemistry; Mercury(II) complex; Crystal structure;

A new two-dimensional HgII coordination polymer containing 5-bis(4-pyridyl)-1,3,4-oxadiazole (bpo) and azide anions, [Hg(μ-bpo)2(N3)2] n , has been synthesized and characterized by elemental analysis, IR-, 1H NMR-, 13C NMR spectroscopy and studied by thermal, fluorescence and X-ray crystallography. The single-crystal X-ray data shows that bpo ligand is bridged via one pyridyl nitrogen and one oxadiazole nitrogen atom, as a novel coordination mode of the bpo ligand.A new two-dimensional HgII coordination polymer containing 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (bpo) and azide anions, [Hg(μ-bpo)2(N3)2] n, has been synthesized and characterized by elemental analysis, IR-, 1H NMR-, 13C NMR spectroscopy and structurally determined by X-ray single-crystal diffraction. The thermal stability of compound [Hg(μ-bpo)2(N3)2] n was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). The single-crystal X-ray data shows that ligand bpo is bridged via one pyridyl nitrogen and one oxadiazole nitrogen atom, as a novel coordination mode of the ligand bpo. Furthermore, the ligand and complex are luminescent in the solid state, with emission maxima in the visible light region (λ max  = 470 nm for both bpo and [Hg(μ-bpo)2(N3)2] n ).
Keywords: Mercury(II); 2,5-Bis(4-pyridyl)-1,3,4-oxadiazole; Coordination polymer; Fluorescence; Thermal properties; X-ray crystallography;

A novel ruthenium(II) complex [Ru(bpy)2(pipipH2)](ClO4)2  · H2O was found to act as a luminescent pH switch through protonation and deprotonation of the bis-imidazole-containing ligand pipipH2 in aqueous solution at room temperature.A novel ruthenium(II) complex, [Ru(bpy)2(pipipH2)](ClO4)2  · H2O (1) (pipipH2  = 2-(4-(1H-phenanthro[9,10-d]imidazol-2-yl)phenyl)-1H- imidazo[4,5-f][1,10] phenanthroline, bpy = 2,2-bipyridine) has been found to act as a luminescent pH switch with extraordinary sensitivity through protonation and deprotonation of the bis-imidazole-containing ligand pipipH2 in aqueous solution at room temperature.
Keywords: Ruthenium(II) complex; Protonation; Deprotonation; Luminescent pH switch;

Synthesis and crystal structure of two novel polymeric PbII compounds: [Pb(phen)(N3)2] n and [Pb(deta)(N3) · (N3)] n by Farzin Marandi; Babak Mirtamizdoust; Ali Akbar Soudi; Hoong-Kun Fun (174-177).
Two novel 1D polymeric Pb(II) complex containing the Pb2-(μ-N3)2 units, [Pb(phen)(N3)2] n (1) and [Pb(deta)(N3) · (N3)] n (2) (deta and phen are the abbreviations of diethylentriamine and 1,10-phenanthroline, respectively) have been synthesized and characterized by single-crystal X-ray diffraction. Compounds of (1) and (2) are six, PbN6, and five, PbN5, coordinated polymers, respectively. Both of them hold hemidirected coordination geometries. To the best of our knowledge, these 1D coordination polymers are the novel Pb2-(μ-N3)2 units of lead(II) compounds and interact with each other via π–π stacking and weak Pb⋯N interactions to create 3D and 2D frameworks.Two novel 1D polymeric Pb(II) complex containing the Pb2-(μ-N3)2 units, [Pb(phen)(N3)2] n (1) and [Pb(deta)(N3) · (N3)] n (2) (deta and phen are the abbreviations of diethylentriamine and 1,10-phenanthroline, respectively) have been synthesized and characterized by single-crystal X-ray diffraction. Compounds of (1) and (2) are six, PbN6, and five, PbN5, coordinated polymers, respectively. Both of them hold hemidirected coordination geometries. To the best of our knowledge, these 1D coordination polymers are the novel Pb2-(μ-N3)2 units of lead(II) compounds and interact with each other via π–π stacking and weak Pb⋯N interactions to create 3D and 2D frameworks.
Keywords: Lead(II); Azide; Coordination polymer;

A new rarely reported TlI one-dimensional coordination polymer containing large tetranuclear metallacycle, Tl2(μ-Htdp)2(μ-H2O)] n (H2tdp = 4,4′-thiodiphenol) (1), has been synthesized, characterized by elemental analysis, IR spectroscopy and structurally determined by X-ray single-crystal diffraction. The single crystal X-ray analysis of compound 1 shows that the complex has been formed from one-dimensional polymer as a result of bridging of Htdp-anions and the thallium atoms contain irregular coordination sphere with stereo-chemically active lone pair.[Tl2(μ-Htdp)2(μ-H2O)] n (H2tdp = 4,4′-thiodiphenol) (1), a new rarely reported TlI one-dimensional coordination polymer with a large tetranuclear metallacycle, has been synthesized, characterized by elemental analysis and IR spectroscopy and its structure determined by single-crystal X-ray diffraction. The thermal stability of compound 1 was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). The single crystal X-ray analysis of compound 1 shows that the complex consists of horseshoe-shaped (μ-Htdp)Tl(μ-H2O)Tl(μ-Htdp) subunits. Solid-state luminescent spectra of the ligand H2tdp and compound 1 indicate emission band with the maximum intensity at 475 and 465 nm upon excitation at 300 nm, respectively.
Keywords: 4,4′-Thiodiphenol; Thallium(I); Coordination polymer; Thermal; Fluorescence;

Structures and electronic spectra of [Pt2(P2O5H2)4X2]4− (X = Cl (1), Br (2) and I (3)) were explored at the ab initio and density functional theory levels. The studies focusing on the σ → σ and π → σ transitions reveal that a reasonable structure associated with an alternative time-dependent density functional is very necessary to obtain the precise transition energy.The structures of [Pt2(P2O5H2)4X2]4− (X = Cl (1), Br (2) and I (3)) were optimized using the ab initio and density functional theory methods. It is shown that the geometry parameters estimated by MP2 and XαVWN are closer to experimental values. We performed the time-dependent density functional theory (TD-DFT) calculations to explore the influence of different density functionals and structures on electronic absorption spectra in solution. The experimental absorptions with the featured σ ( d z 2 ) → σ ∗ ( d z 2 ) and π ( d xz , d yz ) → σ ∗ ( d z 2 ) transitions are well reproduced by the theoretical calculations.
Keywords: Binuclear platinum(III) complex; Electronic spectra; TD-DFT;

The target compound was obtained through hydrothermal reaction route, which exhibits a 3D alternate layered network. This net can be simplified to a binodal 4,6-conneccted (44  · 62)(48  · 66  · 8) topology.This paper describes a novel heteropolynuclear coordination polymer [Cd4Co2(m-BDC)6(HIm)4] n (1) (m-H2BDC = 1,3-benzenedicarboxylic acid, Him = imidazole), which has been hydrothermally prepared and characterized by single-crystal X-ray diffraction, IR, ICP, XRPD, TGA, DSC, and element analysis. The overall architecture is constructed from alternate Co(II) and Cd layers arranged in ABAB mode, and affords a three-dimensional (3D) 4,6-conneccted (44  · 62)(48  · 66  · 8) topological network. Furthermore, magnetic property of 1 has also been studied in the temperature range of 5–300 K.
Keywords: Heteropolynuclear; Alternate layer; 4,6-Connected topology; Thermal property; Magnetic property; Hydrothermal synthesis;

First example of a near-IR photodetector based on neutral [M(R-dmet)2] bis(1,2-dithiolene) metal complexes by M. Carla Aragoni; Massimiliano Arca; Francesco A. Devillanova; Francesco Isaia; Vito Lippolis; Annalisa Mancini; Luca Pala; Gaetano Verani; Tiziano Agostinelli; Mario Caironi; Dario Natali; Marco Sampietro (191-194).
The fabrication and the EQE and time-response characterisation of the first example of a Vis-NIR wavelength sensitive photodetecting device based on a neutral complex belonging to the class [Ni(R-dmet)2] are reported (R-dmet2−  =  N-substituted 2-thioxothiazoline-4,5-dithiolato).We report on the first example of a light signal photodetecting device based on the new class of neutral bis(1,2-dithiolene) complexes [M(R-dmet)2], whose ligand is intermediate between those belonging to the classes dmit2− and R,R′-timdt2− (dmit2−  = 2-thioxo-1,3-dithiole-4,5-dithiolato; R,R′-timdt2−  =  N,N′-disubstituted 2-thioxoimidazoline-4,5-dithiolato; R-dmet2−  =  N-substituted 2-thioxothiazoline-4,5-dithiolato). The device, hosting the active material [Ni(Et-dmet)2] (1) casted on a quartz substrate, acts as a photodetector responsive in a wide spectral range, reaching the appealing near-IR region, and features the highest efficiency values as compared to those based on the dithiolene complexes [Ni(Me,Non-timdt)2] (2) and [Pt(Et,Pent-timdt)2] (3).
Keywords: Ni dithiolenes; NIR; Optoelectronics; Photodetector;

Synthesis of phenanthroline derivative by Suzuki coupling reaction and the use of its ruthenium complex as an optical pH sensor by Hyungoog Nam; Miso Jeong; Ok-Jae Sohn; Jong Il Rhee; Jonghoon Oh; Youngjo Kim; Sunwoo Lee (195-198).
A phenanthroline derivative 5, which has an aniline group, was synthesized by palladium catalyzed Suzuki cross coupling reactions. The ligand, PPh3, gave the highest yield of the product in a K2CO3 base and THF/H2O solvent system. Its ruthenium complex 8 was synthesized under mild conditions. It showed a linear fluorescence intensity response between pH 3.5 and pH 8.5 .A phenanthroline derivative, which has an aniline group, was synthesized by palladium catalyzed Suzuki cross coupling reactions. The aryl phosphine ligand, PPh3, showed higher activity than the alkyl phosphines, P( t Bu)3 and PCy3, in the Suzuki couplings and provided the coupled product, 4-phenyl-7-(4′-amino-biphenyl-4-yl)-[1,10]phenanthroline (5), with 73% yield. Its ruthenium complex, bis(4,7-diphenyl-[1,10]phenanthroline){4-phenyl-7-(4′-amino-biphenyl-4-yl)-[1,10]phenanthroline} ruthenium(II) bis(hexafluorophosphate) (8), was synthesized under mild conditions. This complex showed a linear fluorescence intensity response between pH 3.5 and pH 8.5.
Keywords: Ruthenium; Palladium; Suzuki; Phenanthroline; pH sensor; Fluorescence;

Two monomeric Cd(II) and Zn(II) complexes [M(trtr)2(H2O)4](SiF6) (M = Cd for 1; Zn for 2) were obtained from the reactions of bitriazole ligand 4-[3-(1,2,4-triazolyl)-1,2,4-triazole] with metal fluorosilicate. Two 3-D supramolecular frameworks are constructed by the hydrogen bondings. The fluorescence of 1 and 2 feature the emission peaks at 454 and 348 nm, respectively, originating from the π–π intraligand transition and LMCT.Two monomeric Cd(II) and Zn(II) complexes [M(trtr)2(H2O)4](SiF6) (M = Cd for 1; Zn for 2) were obtained from the reactions of bitriazole ligand 4-[3-(1,2,4-triazolyl)-1,2,4-triazole] with metal fluorosilicate. 3-D supramolecular frameworks are constructed by the hydrogen bondings between the monomeric assemblies and SiF 6 2 - . The fluorescence of 1 and 2 feature the emission peaks at 454 and 348 nm, respectively, originating from the π–π intraligand transition and LMCT, which are related to the triazole rings the metal centers coordinate with.
Keywords: Mononuclear; Zn(II); Cd(II); Crystal structure; 1,2,4-Triazole; Fluorescence;

Phosphate diester hydrolysis promoted by new Cu(II) alkoxide complexes by Hong-Chang Liang; Yonglian Zhang; Marcel M. Hetu (204-208).
Cu(II) complexes of N3 donor pyridyl-amine ligands, bis-(2-pyridin-2-yl-ethyl)-amine (L1), which does not have an alcohol pendant, and 2-[bis-(2-pyridin-2-yl-ethyl)-amino]-ethanol (L2) and 3-[bis-(2-pyridin-2-yl-ethyl)-amino]-propan-1-ol (L3), both containing alcohol pendants, have been synthesized and structurally characterized. The reactivities of these Cu(II) complexes towards promoting bis(p-nitrophenyl)phosphate (BNPP) hydrolysis were investigated, and differences in their hydrolytic activities based on ligand design are explored.Three Cu(II) complexes of N3 donor pyridyl-amine ligands, bis-(2-pyridin-2-yl-ethyl)-amine (L1), which does not have an alcohol pendant, and 2-[bis-(2-pyridin-2-yl-ethyl)-amino]-ethanol (L2) and 3-[bis-(2-pyridin-2-yl-ethyl)-amino]-propan-1-ol (L3), both containing alcohol pendants, have been synthesized and structurally characterized. The reactivities of CuL1 (1), CuL2 (2), and CuL3 (3) for promoting the hydrolysis of bis(p-nitrophenyl)phosphate (BNPP) have been investigated, showing that 3 is much more active (observed second order rate constant k  = 6.1 × 10−1  M−1  s−1 at pH 8.4, 50 °C) than 1 (k  = 9.4 × 10−3  M−1  s−1 at pH 8.4, 50 °C) or 3 (observed second order rate constant k  = 5.2 × 10−3  M−1  s−1 at pH 8.4, 50 °C) at promoting the hydrolysis of BNPP. The much higher reactivity of 3 compared to 2 and 1 may be explained by the higher flexibility of the alkoxide tether in 3, which may allow the nucleophilic alkoxide O-atom in 3 better access to attack a metal-bound BNPP substrate, whereas 2, which has a shorter alkoxide tether, may resort to hydrolyzing the BNPP substrate with a metal-bound hydroxide instead of utilizing its alkoxide moiety because of constraints in the ligand tether. The similar reactivities of 1 and 2 suggest that this is a possible scenario. Another possible explanation for the difference in reactivity between 3 and 2 may be attributed to the alcohol pendant in 3 being better oriented to serve as a proton acceptor from a Cu(II)-bound aqua ligand, which would facilitate its deprotonation and the subsequent nucleophilic attack of the Cu(II)-hydroxide moiety towards the substrate. The reactivities of 2 and 3 towards hydrolyzing BNPP are also compared with that of their Zn(II) analogues, showing that the Cu(II) complexes of the same ligand sets are more hydrolytically active than the corresponding Zn(II) complexes. Single crystal X-ray structures of 1, 2, and 3 are also reported, which show that complexes 2 and 3 form dimers with bridging alkoxide ligands in the solid state, while 1 forms a dimer with bridging chloride ligands in the solid state.

A new mononuclear complex was synthesized with a tridentate ligand containing pyridyl nitrogen, thioether sulfur and a phenolate oxygen donor. When reacted with copper(II) chloride the expected 1:1 metal to ligand complex is formed giving high redox potentials and the characteristic LMCT transitions.The preparation and characterization using UV/Vis spectroscopy and cyclic voltammetry of a tridentate ligand 2-[1′-(4′-(2″-pyridyl)-2′-thiabutyl)]-4-methoxyphenol (HL) and its mononuclear copper(II) complex is presented. Electronic spectra of the complex give intense low energy transitions ascribed as ligand to metal charge transfer (LMCT) transitions. A quasireversible CuII/I redox couple is observed at high potentials due to stabilization of the Cu(I) oxidation state by the thioether sulfur and pyridyl nitrogen coordination.
Keywords: Copper; Tridentate; Pyridyl; Thioether; Phenolate;

Ferromagnetic interactions in zinc(II) coordination complex containing nitronyl nitroxide radicals by Liya Wang; Lufang Ma; Yufang Wang; Bin Zhao; Zonghui Jiang; Daizheng Liao; Shiping Yan (212-215).
A new complex with ferromagnetic formulated as Zn(NIT2-py)3(ClO4)2 was obtained. The units of [Zn(NIT2-py)3]2+are connected as 1-D chain structure by the intermolecular hydrogen bonds. Temperature dependence of susceptibility measurements shows a weak ferromagnetic coupling between NIT2-py radicals with J  = 2.13 cm−1. To our knowledge, the complex is the first example of a zinc(II) complex of nitronyl nitroxide radical with ferromagnetic interaction.A novel complex Zn(NIT2-py)3(ClO4)2(NIT2-py = 2-(2′-pyridyl)-4,4,5,5-tetramethyl-2-imidazoline-1-oxyl-3-oxide) (1) has been synthesized and characterized structurally and magnetically. The metal coordination sphere is fully occupied by three chelating nitroxide ligands, showing a distorted octahedral geometry. Temperature dependence of susceptibility measurements shows a weak ferromagnetic coupling between NIT2-py radicals with J  = 2.13 cm−1. The field dependence of the magnetization further confirms that the ground state of the compound S  = 3/2 results from ferromagnetic interactions within the complex 1.
Keywords: Crystal structure; Nitronyl nitroxide radical; Zinc(II) complex; Ferromagnetic properties;

Syntheses, properties and biological activity of organogermanium substituted heteropolytungstates by Jianxin Li; Rongxin Tan; Rui Li; Xiaohong Wang; Enmin Li; Fengying Zhai; Shengdong Zhang (216-219).
Six new compounds [(RGe)XW11O39] n (R = HOOCCH2CH2, HOOCCH2(m-NO2C6H4)CH); X = Ge, Si, P) have been prepared and their Keggin structures determined by elementary analysis, IR, UV, 1H NMR and 183W NMR spectrometry. The results show that the complexes retain Keggin structure with organogermanium group grafting on the polyoxometalate surface. The complexes exhibit antitumoral activity in vitro as shown by MTT experiment.Six new compounds [(RGe)XW11O39] n (R = HOOCCH2CH2, HOOCCH2(m-NO2C6H4)CH); X = Ge, Si, P) have been prepared and their Keggin structures determined by elementary analysis, IR, UV, 1H NMR and 183W NMR spectrometry. The results show that the complexes retain Keggin structure with organogermanium group grafting on the polyoxometalate surface. The complexes exhibit antitumoral activity in vitro as shown by MTT experiment.
Keywords: Synthesis; Organogermanium; Polyoxometalates; Antitumoral activity;

Synthesis and characterizations of a magnesium metal–organic framework with a distorted (10, 3)-a-net topology by Shengqian Ma; Jacqueline A. Fillinger; Michael W. Ambrogio; Jing-Lin Zuo; Hong-Cai Zhou (220-222).
A (10, 3)-a magnesium metal–organic framework exhibiting second harmonic generation has been synthesized under solvothermal reaction conditions.A magnesium metal–organic framework with a distorted (10, 3)-a-net topology has been synthesized under solvothermal conditions, and characterized by X-ray structure determination, thermogravimetric analysis, X-ray powder diffraction, IR, and nonlinear optical studies.
Keywords: Metal–organic framework; Magnesium; (10, 3)-a; Noncentrosymmetric; Second-harmonic generation;

Synthesis, structure and properties of (4,4′-H2bipy)[HgBr4] · H2O with strong fluorescence by Wen-Tong Chen; Xi-Rui Zeng; Xiao-Niu Fang; Xin-Fa Li; Li-Min Liu (223-225).
A novel compound (4,4′-H2bipy)[HgBr4] · H2O with strong blue fluorescence has been synthesized via hydrothermal reaction. The crystal structure is characteristic of an isolated structure. Optical absorption spectrum shows that the title compound may be a candidate for potential photoelectric material. IR, SEM/EDS and TG-DTA are also presented.(4,4′-H2bipy)[HgBr4] · H2O (1), has been synthesized via hydrothermal reaction. The title compound features an isolated structure, based on discrete 4,4′-H2bipy moieties, lattice water molecules and tetrahedral mercury atoms terminally coordinated by four bromine atoms. The 4,4′-H2bipy moieties, lattice water molecules and tetrabromo-mercury dianions are linked via hydrogen bonds. Optical absorption spectrum reveals that the presence of an optical gap of 2.53 eV, indicating that compound 1 exhibits a semiconductor property. Photoluminescent investigation reveals that the title compound displays a strong blue-light emission, which maybe originates from π → π charge-transfer interaction of 4,4′-H2bipy. IR, SEM/EDS and thermogravimetry-differential thermal analyses (TG-DTA) are also presented.
Keywords: Crystal structure; Fluorescence; Halide; Mercury; Semiconductor;

Photoproperties of silver sulfadiazine by Horst Kunkely; Arnd Vogler (226-228).
Dry silver sulfadiazine (AgSD) is not light sensitive but shows a greenish-blue r.t. photoluminescence at λ max  = 482 nm which is suggested to originate from an IL triplet. In the presence of water AgSD undergoes a partial hydrolysis with the formation of free sulfadiazine (HSD) which has been previously shown to be photoreactive. Moreover, irradiation of an aqueous suspension of AgSD leads also to the photoreduction of Ag+ to elemental silver. This photolysis might explain the origin of argyria which can occur when AgSD in contact with human skin is exposed to sun light.Dry silver sulfadiazine (AgSD) is not light sensitive but shows a greenish-blue r.t. photoluminescence at λ max  = 482 nm which is suggested to originate from an IL triplet. In the presence of water AgSD undergoes a partial hydrolysis with the formation of free sulfadiazine (HSD) which has been previously shown to be photoreactive. Moreover, irradiation of an aqueous suspension of AgSD leads also to the photoreduction of Ag+ to elemental silver. This photolysis might explain the origin of argyria which can occur when AgSD in contact with human skin is exposed to sun light
Keywords: Electronic spectra; Luminescence; Phosphorescence; Intraligand states; Photochemistry; Silver; Sulfadiazine; Argyria;

Multicomponent ligands incorporating triazine-based coordinating motifs with pendant phenanthryl and phenyl–phenanthryl groups exhibit intra-ligand charge-transfer states, which are modified by metal ion coordination .Ru(II) and Zn(II) complexes of multicomponent ligands have been synthesised and characterised incorporating triazine-based coordinating motifs with pendant phenanthryl and phenyl–phenanthryl groups. At room temperature the ligands emit from intra-ligand charge-transfer (ILCT) states, the energy of which may be lowered significantly by metal–ion coordination (e.g. Zn(II)). The ILCT state is efficiently quenched in the Ru(II) complexes by energy transfer to a low-lying metal–ligand charge-transfer 3MLCT state.
Keywords: Triazine ligands; Ruthenium complexes; Zinc complexes; Phenanthrene; Tridentate ligands; Structural studies;

Copper(II) complexes with chiral reduced Schiff bases: Helical self-assembly via intermolecular C–H⋯O interactions by Vamsee Krishna Muppidi; Sunirban Das; Pallepogu Raghavaiah; Samudranil Pal (234-238).
Syntheses, characterization and X-ray structures of copper(II) complexes with chiral reduced Schiff bases are described. Intermolecular C–H⋯O interaction assisted self-assembly of each of these complex molecules provides helical superstructure.Copper(II) complexes having the general formula [Cu(L n )2] with the N,O-donor reduced Schiff bases N-(2-hydroxy-5-X-benzyl)-(R)-α-methylbenzylamine and N-(2-hydroxy-5-X-benzyl)-(S)-α-methylbenzylamine (X  = Cl and Br) (HL n ) are described. These chiral complexes crystallize in the noncentrosymmetric P212121 (X  = Cl) and P21 (X  = Br) space groups. In each case, self-assembly via intermolecular C–H⋯O interaction leads to a supramolecular helical superstructure.
Keywords: Copper(II) complexes; Reduced schiff bases; Chiral; Crystal structures; Helical self-assembly;

The novel silylated diene 3, a by-product from the reaction of PhSiCl3 with Me3SiCl and lithium in THF at low temperatures was isolated and its structure has been confirmed by X-ray crystallography. The formation of 3 formally arises from a consecutive chemo-reductive cleavage of the aromatic C=C double bond in the phenyl-tris(trimethylsilyl)silane (1a) by action of lithium and trimethylchlorosilane.The new compounds 1,1,6,6-tetrakis(trimethylsilyl)-3-tris(trimethylsilyl)silyl-hexa-2,4-diene (3) and 2,4,6-trimethyl-3,4-bis(trimethylsilyl)-1-tris(trimethylsilyl)silyl-cyclohexa-1,5-diene (4b) have been isolated as by-products from the reaction of PhSiCl3 or MesSiCl3 with Me3SiCl and lithium in THF at low temperatures. The X-ray crystal structures of 3 and 4b are reported.
Keywords: Reductive silylation; Arenes; X-ray crystallography; Silanes; Dienes;

A red emitting discotic liquid crystal containing the cyclopalladated nile red chromophore by Mauro Ghedini; Daniela Pucci; Alessandra Crispini; Anna Bellusci; Massimo La Deda; Iolinda Aiello; Teresa Pugliese (243-246).
A new red emitting discotic metal containing liquid crystal, NIRPAC, exhibiting a columnar phase over a broad temperature range has been successfully synthesised by following a bit-by-bit procedure.A new red emitting (λ em  = 610 nm) discotic metal containing liquid crystal, NIRPAC, exhibiting a columnar phase over a broad temperature range (35–173 °C) has been successfully synthesised by an appropriate functionalisation of the cyclopalladated nile red molecular fragment.
Keywords: Discotic liquid crystal; Cyclopalladated complexes; Luminescence; Nile Red; Metallomesogens;

Reaction of silver nitrate with 1,4-bis(2-quinolyloxy)benzene gave a one-dimensional coordination polymer in which there is extensive π–π stacking of the quinoline units.Reaction of silver nitrate with 1,4-bis(2-quinolyloxy)benzene (4) gave a one-dimensional coordination polymer (5) in which there is extensive π–π stacking of the quinoline units.
Keywords: Silver; Coordination polymer; π–π Stacking; N ligands; Quinoline;

An extended 1D network formed by complementary hydrogen bonding between Pt(IV)-complexed tetrazoles by Anatoly V. Khripun; Vadim Yu. Kukushkin; Grigory I. Koldobskii; Matti Haukka (250-254).
Reaction of trans-[PtCl4(EtCN)2] with 5-methyl-1H-tetrazole in MeNO2 solution leads to the formation of the first metal complex containing the N1-ligated tetrazole, viz., trans-[PtCl4(5-Me-4H-tz-κN1)2], which displays in the solid state a novel type of complementary hydrogen-bonding between the –NH– and –N= moieties of the heterocycles from the neighboring molecules, thus forming an extended 1D network.The first metal complex containing the N1-ligated tetrazole, viz., trans-[PtCl4(5-Me-4H-tz-κN1)2] (1), has been prepared by the reaction between trans-[PtCl4(EtCN)2] and 5-methyltetrazole and characterized by elemental analyses, FAB+-MS, IR, and 1H, 13C{1H}, 195Pt NMR spectroscopies and also by X-ray diffraction. In the solid state, 1 displays a novel type of complementary hydrogen-bonding between the –NH– and –N=moieties of the heterocycles from the neighbouring molecules, thus forming an extended 1D network.
Keywords: Platinum(IV) complexes; N1-ligated tetrazoles; Tetrazole complexes; 1D network; Complementary hydrogen-bonding; Linkage isomerization;