Inorganic Chemistry Communications (v.10, #4)

Contents List (iii-xi).

A new water-soluble copper phthalocyanine, 2,9,16,23-tetrakis(4-(1-naphthoxy-4-sulfonic acid sodium salt)) phthalocyaninato copper NhtCuPc was synthesized and its electrochemical and spectroelectrochemical behavior were investigated in DMSO solution.A new water-soluble copper phthalocyanine, 2,9,16,23-tetrakis(4-(1-naphthoxy-4-sulfonic acid sodium salt)) phthalocyaninato copper NhtCuPc, where Nht indicates naphthoxy-4-sulfonic acid sodium salt, was synthesized and its electrochemical and spectroelectrochemical behavior were investigated in DMSO solution. The in situ spectroelectrochemical studies showed that the neutral complex exhibited the characteristic spectral changes corresponding to mono-anionic [NhtCuPc(3-)] and di-anionic [NhtCuPc(4-)] 2 species having long-term stability during reduction processes.
Keywords: Phthalocyanines; Complexation; Electrochemistry; Spectroelectrochemistry;

First example of antimoniated Schiff bases: Hypervalent Sb ← N(sp2) bonds by Pankaj Sharma; Diego Pérez; Jaime Vázquez; A. Toscano; René Gutiérrez (389-392).
The first example of antimoniated Schiff bases viz. 1-[2-(bis-{2-[(1-R-p-tolylethylimino)methyl]phenyl}stibanyl)benz-E-ilidene]-(1-R-p-tolylethyl)amine (1) and tris[(R)-2-benzyliden-2-yl-amino)butan-1-ol]stibine (2) containing imino groups at the ortho position of aryl ring have been synthesized and characterized. The compounds were obtained by the reaction of tris(o-formylphenyl)stibine with R-4-dimethyl benzyl amine or (R)-2-aminobutan-1-ol, respectively. These chiral antimony based Schiff bases were characterized by IR, mass, 1H, 13C, NMR spectroscopy. The X-ray crystal structures of these two Schiff bases show hypervalent interactions between antimony and sp2 nitrogen atoms. Additionally compound 2 shows intramolecular Sb–O interaction also giving eight-coordination of antimony, both of these observations are uncommon in literature. These two compounds 1 and 2 show helicoidal chirality, which is a very new concept in antimony chemistry.The first example of antimoniated Schiff bases viz. 1-[2-(bis-{2-[(1-R-p-tolylethylimino)methyl]phenyl}stibanyl)benz-E-ilidene]-(1-R-p-tolylethyl)amine (1) and tris[(R)-2-benzyliden-2-yl-amino)butan-1-ol]stibine (2) containing imino groups at the ortho position of aryl ring have been synthesized and characterized. The compounds were obtained by the reaction of tris(o-formylphenyl)stibine with R-4-dimethyl benzyl amine or (R)-2-aminobutan-1-ol, respectively. These chiral antimony based Schiff bases were characterized by IR, mass, 1H, 13C, NMR spectroscopy. The X-ray crystal structures of these two Schiff bases show hypervalent interactions between antimony and sp2 nitrogen atoms. Additionally compound 2 shows intramolecular Sb–O interaction also giving eight-coordination of antimony, both of these observations are uncommon in literature. These two compounds 1 and 2 show helicoidal chirality, which is a very new concept in antimony chemistry.
Keywords: Antimoniated; Hypervalent antimony; Sb–N(sp2)bonds; Eight-coordination; Helical chirality;

New tris(3-phenyl-4-aroyl-5-isoxazolonate)terbium(III) complexes have been synthesized and characterized by various spectroscopic techniques. Due to an efficient energy transfer from the heterocyclic β-diketonate ligand to the central Tb3+, these complexes show a strong emission corresponding to Tb3+ 5D47F J (J  = 6, 5, 4, 3) transitions, with 5D47F5 (545 nm) green emission as the most prominent one.New tris(3-phenyl-4-aroyl-5-isoxazolonate)terbium(III) complexes have been synthesized and characterized by various spectroscopic techniques. Due to an efficient energy transfer from the heterocyclic β-diketonate ligand to the central Tb3+, these complexes show a strong emission corresponding to Tb3+ 5D47F J (J  = 6, 5, 4, 3) transitions, with 5D47F5 (545 nm) green emission as the most prominent one. The overall quantum yields and luminescent lifetimes of these complexes were found to be promising as compared to previously reported terbium-1-phenyl-3-methyl-4-acyl-5-pyrazolonate complexes.
Keywords: Tb3+; 3-Phenyl-4-aroyl-5-isoxazolonate complexes; Crystal structure; Luminescence;

The first heterometal tetranuclear complex with alternating azido and phenoxo bridges, [Mn2Ni2(MeOSalen)21,1-N3)2(N3)2] was synthesized and characterized. There is a ferromagnetic interaction between the azido- bridged Mn(II) ions while the Ni(II) ions are diamagnetic.The first heterometal tetranuclear complex with alternating azido and phenoxo bridges, [Mn2Ni2(MeOSalen)21,1-N3)2(N3)2] (MeOSalenH2  = bis(3-methoxy)salicylideneimine), was synthesized and structurally characterized by X-ray crystallography and spectroscopic methods. Magnetic studies suggest there is a ferromagnetic interaction between the μ1,1-azido-bridged Mn(II) ions with J  = +2.11 cm−1, while the Ni(II) ions are diamagnetic in the tetranuclear system.
Keywords: Heterometallic complex; Schiff-base; Manganese(II); Nickel(II); Crystal structure; Magnetic properties;

A new trinuclear zinc(II) complex possessing five- and six-coordinated central ions and its photoluminescent property by Tianzhi Yu; Kai Zhang; Yuling Zhao; Changhui Yang; Hui Zhang; Duowang Fan; Wenkui Dong (401-403).
A trinuclear zinc complex has been synthesized, in which three Zn(II) ions are coordinated by two tetradentate Schiff base ligands and two acetates. Two zinc ions show the coordination number of five and the third one has the coordination number of six. The complex shows blue-green emission.A aromatic Schiff base ligand, N,  N′-bis((4, 4′-diethylamino)salicylidene)-1, 2-phenylenediamine (H2L), and its trinuclear zinc(II) complex, Zn3L2(CH3COO)2, were synthesized. The X-ray crystal structure of the complex reveals that two zinc ions show the coordination number of five and the third one has the coordination number of six. The complex exhibits blue-green emission as the result of the fluorescence from the intraligand emission excited state.
Keywords: Trinuclear zinc complex; Aromatic Schiff base ligand; Crystal structure; Photoluminescent property;

Synthesis, crystal structure and urease inhibitory activities of Schiff base metal complexes by Da-Hua Shi; Zhong-Lu You; Chen Xu; Qiang Zhang; Hai-Liang Zhu (404-406).
Six novel transition metal complexes with Schiff base were synthesized and crystallographically characterized. Three of them showed potent inhibitions on jack bean urease. Schiff base Mn(II) complex [Mn3(SALPD)2(OAc)2] (2) possessed the best jbU inhibitory activity with IC50 of 8.30 ± 0.93 μM, which was better than those of the corresponding ligand and control ion.Six new transition metal complexes (16) with Schiff base were synthesized and crystallographically characterized. Their urease inhibitory activities were evaluated. Three of them showed potent inhibitions against jack bean urease. Mn(II) complex (2) possessed the best jbU inhibitory activity with IC50 of 8.30 ± 0.93 μM, which was much better than those of the corresponding ligand and control ion. The investigation on the stability constants and the structure-activity relationships of the complexes indicated that the complexes interacted with the enzyme in the whole complex forms rather than the free ions.
Keywords: Schiff base complexes; Crystal structures; Jack bean urease; Inhibitor;

Formation of N-coordinated 4H-benzo[d][1,3]oxazine from 2-(trimethylsiloxymethyl)- and 2-(hydroxymethyl)-phenyl isocyanides promoted by dirhodium(II) acetate by Marino Basato; Andrea Biffis; Gianluca Martinati; Mauro Polo; Luca Ronconi; Cristina Tubaro; Rino A. Michelin; Paolo Sgarbossa; Silvia Mazzega Sbovata (407-409).
The neutral dirhodium complexes [Rh2(OAc)4(CNC6H4-2-CH2OR)2] (R = OSiMe3, H) undergo an intramolecular ligand rearrangement via oxygen attack to the coordinated isocyanide carbon atom giving the benzoxazine complex ▪.The neutral dirhodium(II) acetate [Rh2(OAc)4] and the related cationic complex [Rh2(OAc)2(MeCN)6](BF4)2 react with 2-(trimethylsiloxymethyl)phenyl isocyanide (I) and/or 2-(hydroxymethyl)phenyl isocyanide (II) to give the corresponding adducts, in which the entering isocyanide occupies the axial position at the two rhodium centres. These complexes are stable in toluene, but they evolve in chloroform as a consequence of an intramolecular ligand rearrangement via oxygen attack to the coordinated carbon atom. With the neutral dirhodium acetate species the cyclization reaction affords the well characterized benzoxazine complex ▪ (4), whereas the cationic acetonitrile derivative rapidly evolves into a complex mixture.
Keywords: Rhodium(II); Functionalized isocyanides; Benzo[d][1,3]oxazine complex;

Two novel lead-carboxylate complexes based on nicotinic acid N-oxide: Synthesis, crystal structures and luminescent properties by Ya-Hui Zhao; Zhong-Min Su; Yong Wang; Yao-Mei Fu; Si-Dong Liu; Peng Li (410-414).
Reaction of lead(II), nicotinic acid N-oxide (NNO) and different carboxylate acid (fumaric acid or 1,3,5-benzenetricarboxylic acid) gives a 1D zig-zag chain and a 3D network structure. Moreover, two compounds both exhibit good room-temperature phosphorescence emissions.Two new lead-carboxylate complexes based on nicotinic acid N-oxide ligand, [Pb(NNO)(FA)0.5] (1) (HNNO = nicotinic acid N-oxide, FA = fumaric acid) and [Pb2(NNO)(BTC)] (2) (H3BTC = 1,3,5-benzenetricarboxylic acid) were hydrothermally synthesized and characterized by the elemental analyses, IR spectra and single crystal X-ray diffraction. Significant phosphorescent properties of two compounds were observed at room temperature.
Keywords: Hydrothermal reaction; N-oxide; Lead complex; Luminescent property;

This paper describes an unusual coordination polymer, M44-O)(bipy)(m-BDC)3 (M4  = Zn2.36Co1.64, bipy = 4,4′-bipyridine, m-H2BDC = 1,3-benzenedicarboxylic acid) (1), which contains a M4O(O2C)6 secondary building unit with an unusual inclined interpenetrated (4, 4) topology, and is a rare combination of the two most successful approaches to coordination polymer design: generation of metal carboxylate SBUs and the use of pyridyl donor bridges.The objective of this paper is to describe an unusual coordination polymer, M44-O)(bipy)(m-BDC)3 (sM4  = Zn2.36 Co1.64, bipy = 4,4′-bipyridine, m-H2BDC = 1,3-benzenedicarboxylic acid) (1), which has been hydrothermally synthesised and characterized by single-crystal X-ray diffraction, XRPD, IR, TGA, ICP, atomic absorption, and element analysis. 1 crystallizes in the P42/mnm space group and contains a M4O(O2C)6 secondary building unit (SBU) with an inclined interpenetrated (4, 4) topology, and is a rare combination of the two most successful approaches to coordination polymer design: generation of metal carboxylate SBUs and the use of pyridyl donor bridges. Moreover, complex 1 exhibits intense fluorescence at about 424 nm (λ ex  = 312 nm) in the solid state.
Keywords: Inclined interpenetration; Heteropolynuclear; M4O(O2C)6 SBUs; Fluorescent property; Hydrothermal synthesis;

Formation of one-dimensional metal–water chain containing discrete water octamers by Xue-Qin Song; Wei Dou; Wei-Sheng Liu; Jing-Xin Ma (419-422).
We have observed discrete water octamers which are trapped not only by an organic molecule via hydrogen bonds but also by the metal ion via coordination interactions. The cooperative association among the metal ion, the water molecule, and the organic molecule plays a crucial role in the formation of multidimensional architecture and the water cluster.Discrete water octamers containing 1D metal–water chains have been observed in the complex of [Tb2(bpdc)(Pic)2(OH2)12](Pic)2  · 4H2O · (CH3OH)2 (Pic = picrate, bpdc = 2,2′-bipyridine-3,3′-dicarboxylate) (1). The water clusters are trapped by the cooperative association of coordinate interactions as well as hydrogen bonds. The intermolecular interaction is robust enough to really act as a ‘supramolecular glue’ to assemble the binuclear coordination complex and picratol into three-dimensional arrays.
Keywords: Lanthanide picrate complex; Crystal structure; Water-cluster; Hydrogen bond; Supramolecular structure;

Nitrilotriacetate behaves as a trigonal assembler in its complex with uranyl ions, giving rise to ladder-like ribbons in which each ligand has an unusually low coordination number of three.Reaction of uranyl nitrate with N-(2-acetamido)iminodiacetic acid (ADA) under hydrothermal conditions resulted in the hydrolysis of the amide group and the isolation of the complex [(UO2)(HNTA)(H2O)2], in which each nitrilotriacetate ligand, protonated at the N site, bridges three metal atoms to give rise to infinite ladder-like ribbons built from 2:2 metallacycles.
Keywords: Uranyl ion; Uranium-organic framework; Nitrilotriacetic acid; Hydrothermal synthesis; Crystal structure;

Synthesis, structure and properties of a novel metal tellurobromide – Hg2TeBr3 by Wen-Tong Chen; Xin-Fa Li; Qiu-Yan Luo; Ya-Ping Xu; Guang-Pei Zhou (427-431).
A novel metal chalcogenide Hg2TeBr3 was synthesized via solid-state reactions. The crystal structure is characterized by a 2D layer structure, comprising of interconnected Hg-centered tetrahedral and trigons. Optical absorption spectra reveal the presence of sharp optical gap of 2.03 eV. The title compound is thermally stable up to 173 °C.A novel metal tellurobromide Hg2TeBr3 (1) was obtained by solid-state reactions and structurally characterized. Compound 1 is characterized by a 2D layer structure. Optical absorption spectra of 1 reveal the presence of sharp optical gap of 2.03 eV. TG-DTA measurement shows that compound 1 is thermally stable up to 173 °C. The composition of 1 is well confirmed by the semiquantitative microscope analysis.
Keywords: Chalcogenide; Halide; Mercury; SEM/EDS; Tellurium;

Synthesis, crystal structure and nonlinear optical property of cadmium(II) and copper(II) complexes with novel chiral ligand by Yue-Wei Sheng; Yan Wang; Taka-Aki Okamura; Wei-Yin Sun; Norikazu Ueyama (432-436).
Two novel metal-organic frameworks (MOFs) [Cd(3-MPCA)2  · H2O] · 5.5H2O (1) and [Cu(3-MPCA)2  · H2O] · 4H2O (2) [3-MPCA = 1,2,2-trimethyl-3-(pyridin-3-ylmethylcarbamoyl)cyclopentanecarboxylate] with homochiral one-dimensional (1D) chain structure were hydrothermally synthesized and characterized by X-ray crystallography. Nonlinear optical measurements on powdered sample of 1 and 2 revealed that they display second-harmonic-generation (SHG) response of 0.8 and 0.3 times of that for urea, respectively.Two novel metal-organic frameworks (MOFs) [Cd(3-MPCA)2  · H2O] · 5.5H2O (1) and [Cu(3-MPCA)2  · H2O] · 4H2O (2) [3-MPCA  = (1R, 3S)-1,2,2-trimethyl-3-(pyridin-3-ylmethylcarbamoyl)cyclopentanecarboxylate] were hydrothermally synthesized and characterized by X-ray crystallography. Complexes 1 and 2 are homochiral and have similar one-dimensional (1D) chain structure, which are further linked by strong hydrogen bonds to give 3D architectures. There are oxygen hexmers and heptamers from water molecules and carbonyl group in 1 with O⋯O distances and O–O–O angles comparable to the corresponding values in ice. Nonlinear optical measurements on powdered sample of 1 and 2 revealed that they display second-harmonic-generation (SHG) response of 0.8 and 0.3 times of that for urea, respectively.
Keywords: Chiral ligand; Cadmium(II) complex; Copper(II) complex; Nonlinear optical property;

A new mixed-valence copper(I, II) coordination polymer with 1-D chain structure by Qing Yu; Li-Gang Zhu; He-Dong Bian; Ji-Hua Deng; Xiao-Ge Bao; Hong Liang (437-439).
A new mixed-valence copper(I, II) coordination polymer, { [ Cu 2 I Cu 2 II I 2 L 4 ] · 4 DMF } n 1 (HL =  N′-(2-methylene pyridine)isonicotinohydrazide), was synthesized by N′-((N-oxide- pyridin-2-yl)methylene)isonicotinohydrazide and cuprous iodide.A new mixed-valence copper(I, II) coordination polymer, { [ Cu 2 I Cu 2 II I 2 L 4 ] · 4DMF } n 1 (HL =  N′-(2-methylene pyridine)isonicotinohydrazide), was synthesized by N′-((N-oxide- pyridin-2-yl)methylene)isonicotinohydrazide and cuprous iodide. Complex 1 exhibit a one-dimensional structure built up from mixed valence units of Cu 2 I Cu 2 II L 4 linked by iodide anions. The coordinated environments of Cu(II) and Cu(I) are distorted octahedron and tetrahedron, respectively.
Keywords: Mixed valence; Copper; Coordination polymers; Oxidation reactions; Hydrothermal reactions;

A microporous chiral complex KMn2[(L-C4H2O6)2B] · 3H2O was synthesized solvothermally in the presence of l-tartaric acid. In this framework, Mn2+ ions exhibit distorted octahedral coordination and the tartrate group is bonded to the B atom as a bidentate ligand via oxygen atoms of neighbouring hydroxyl groups.A microporous chiral complex KMn2[(L-C4H2O6)2B] · 3H2O was synthesized solvothermally in the presence of l-tartaric acid. In this framework, Mn2+ ions exhibit distorted octahedral coordination and the tartrate group is bonded to the B atom as a bidentate ligand via oxygen atoms of neighbouring hydroxyl groups.

A new selective fluorescent chemosensor for Cu(II) ion based on zinc porphyrin-dipyridylamino by Yan-Qin Weng; Ying-Lai Teng; Fan Yue; Yong-Rui Zhong; Bao-Hui Ye (443-446).
A new fluorescent sensor based on zinc porphyrin-dipyridylamino displays high selectivity for Cu2+ and exhibits fluorescence quenching upon binding of Cu2+ with an “on–off” type switching property. Its fluorescence can be revived by addition of EDTA disodium solution.A new fluorescent chemosensor 5-(p-N,N′-bis(2-pyridyl)amino)phenyl-10,15,20-tris(p-methoxyphenyl)porphyrin zinc has been designed and synthesized by the Ullmann-type coupling. It displays high selectivity for Cu2+ ion and exhibits fluorescence quenching upon binding of Cu2+ ion with an “on–off” type fluoroionophoric switching property, and its fluorescence can be revived by addition of EDTA disodium solution.
Keywords: Ullmann-type coupling; Porphyrin; Fluorescence sensor; Cu2+ ion;

Synthesis and characterization of nickel phosphonopropionate hybrid materials by Zhenxia Chen; Linhong Weng; Dongyuan Zhao (447-450).
Structure I features a layer consisting of [Ni(HO3PC2H4COO)(H2O)] n chains and 4,4′-bipyridine, which stacks in an ABAB sequence and interacts with each other by hydrogen bonds.Hydrothermal reaction of nickel acetate with 3-phosphonopropionic acid and 4,4′-bipyridine resulted in two novel phosphonate compounds Ni(HO3PC2H4COO)(4,4′-bpy)(H2O) · 0.5(4,4′-bpy) (bpy = bipyridine) (I) and Ni(O3PC2H4COOH)(4,4′-bpy)(H2O)3  · H2O (II). Single-crystal X-ray studies reveal that self-assemblies between the ligands and metal ion result in layer (I) and chain (II) structures. Magnetic measurement of I indicate there are ferromagnetic couplings between adjacent Ni2+ ions (C  = 1.29 cm3  mol−1  K and θ  = 2.25 K).
Keywords: Nickel phosphonates; Crystal structure; Hydrothermal synthesis; 4,4′-Bipyridine;

By administrating a reaction of N,  N′-[(2,3,5,6-tetrafluoro-1,4-phenylene)bis(methylene)]-bis(4-pyridinecarboxamide) (tfpbbp) with Zn(Ac)2  · 2H2O, a novel 1-D metal–organic polymer [Zn(tfpbbp)(Ac)2] n (1) has been synthesized via metal ion-ligand coordination and structurally characterized. The self-assembly of polymer (1), involving hydrogen bonding interactions, renders an interesting three-dimensional porous structure. In addition, the thermal and solid-state photoluminescent properties of the new material have also been studied.A zinc metal–organic framework [Zn(tfpbbp)(Ac)2] n (1) has been prepared by reacting N,  N′-[(2,3,5,6-tetrafluoro-1,4-phenylene)bis(methylene)]bis(pyridine-4-carboxamide) (tfpbbp) with Zn(Ac)2  · 2H2O and characterized by single crystal X-ray diffraction and TGA analysis. Single crystal X-ray diffraction analysis indicates that in solid-state (1) is a 1-D zigzag chain, which further self-assembles into a 3-D supramolecular porous structure through hydrogen bonding interactions. The polymer (1) exhibits photoluminescent property at room temperature.
Keywords: Metal–organic polymer; Crystal structure; Porous; Hydrogen bonding; Thermal study; Fluorescence;

Layered inclusion of [Na6(H2O)] in a [Ni2]6 pore, in which six Na+ ions configure in chair-shape, matching the peripheral hexamer [Ni2]6 ringHydrothermal reactions of pyridyl-2,6-dicarboxylic acid (H2PDC) and NiCl2  · 6H2O in the presence of NaOH and KOH, respectively afforded the products, {[Ni(PDC)(Cl)](Na)(H2O)/3} n (1) and K2[Ni(PDC)2] · 7H2O (2), of which 1 was characterized consisting of 3-D porous framework and [Na6(H2O)]6+ inclusions, and 2 was a mononuclear complex with potassium hydrate as counterion.
Keywords: Porous structure; Pyridyl-2,6-dicarboxylic acid; Ion-molecule inclusion;

Neutral dimeric copper–sparfloxacin conjugate having butterfly motif with antiproliferative effects against hormone independent BT20 breast cancer cell line by Dipti Shingnapurkar; Ray Butcher; Zahra Afrasiabi; Ekkhard Sinn; Fakhara Ahmed; Fazlul Sarkar; Subhash Padhye (459-462).
A neutral dimeric copper conjugate of sparfloxacin, having butterfly scaffold shows 10-fold enhancement in its antiproliferative activity against hormone independent BT20 breast cancer cells.A neutral dimeric copper conjugate of sparfloxacin and its phenanthroline adduct show considerable enhancement in their antiproliferative activities against hormone independent BT20 breast cancer cells.
Keywords: X-ray crystal structure; Sparfloxacin; Phenanthroline adduct; Copper dimer; Breast cancer;

A new hetero-metallic cluster {CpIr[S2C2(B10H10)]}2Mo(CO)2 (2) has been synthesized and structurally characterized, and their third-order nonlinear optical (NLO) properties have been investigated by Z-scan technique. The results indicate that 2 exhibit good NLO absorption and self-focusing effects. The hyperpolarizability γ value is calculated to be 2.60 × 10−29  esu for 2.A hetero-metallic cluster {CpIr[S2C2(B10H10)]}2Mo(CO)2 (2) has been synthesized and structurally characterized, and their third-order nonlinear optical (NLO) properties have been investigated by Z-scan technique. The results indicate that 2 exhibit good NLO absorption and self-focusing effects. The hyperpolarizability γ value is calculated to be 2.60 × 10−29  esu for 2.
Keywords: Iridium; Molybdenum; Carborane; Molecular structure; NLO properties;

The complex [Cd2(phen)4(p-phth)(H2O)2] (p-phth) · 10H2O (1) has been synthesized. In 1 a novel 2D supramolecular structure containing water octamer and tetramer was formed. The water and organic molecules play an important role in the formation of the water cluster and dual host–guest architecture.The complex [Cd2(phen)4(p-phth)(H2O)2](p-phth) · 10H2O (1) has been synthesized by the reaction Cd(NO3)2 with phen and p-phth (where phen = 1,10-phenanthroline, p-phth =  p-phthalic acid) in a solution of ethanol and distilled water. The crystal structure was characterized by X-ray single-crystal diffraction and infrared spectrum. In 1, a novel 2D supramolecular structure was formed, containing water octamer and tetramer.
Keywords: Water chemistry; Supramolecular; Self-assembly;

Thanks to the unexpected hetero acidobasic reaction between the [ReO(salen)OMe] and Y(hfac)3  · 2H2O, a linear tetranuclear complex of formula {[Re(salen)]2O3[Y(hfac)3(H2O)]2}(CHCl3)2(CH2Cl2)2is designed and characterized by X-ray diffraction. It can be used as a model to build paramagnetic structures with the Ln(hfac)3  · 2H2O family.Single crystals of a Y(III)–Re(V)(salen) tetranuclear complex have been obtained by the reaction between the [ReO(salen)(OMe)] and Y(hfac)3  · 2H2O compounds (where salen2− is the N,N-ethan-1,2-diylbis(salicylidenamine) ligand and hfac is the 1,1,1,5,5,5-hexafluoroacetylacetonate ligand). This crystallizes in the triclinic, space group P 1 ¯ (No. 2). The lattice parameters are a  = 12.222(5) Å, b  = 12.783(5) Å, c  = 15.222(4) Å, α  = 86.276(5)°, β  = 82.220(5)°, γ  = 82.396(5)°, V  = 2332.9(15) Å3 with Z  = 2. The crystallographic structure of the {[Re(salen)]2O3 [Y(hfac)3(H2O)]2}(CHCl3)2(CH2Cl2)2 tetranuclear complex is composed of two terminal Y(hfac)3(H2O) moieties bridged by the linear central {[ReO(salen)]2O} entity.

A new hemidirected lead(II) complex converted into holodirected by secondary Pb–N interactions by Yu-Zhou Yuan; Jian Zhou; Xing Liu; Li-Heng Liu; Kai-Bei Yu (475-478).
A new extended 2-D lead(II) coordination polymer [Pb2(ins)2(CH3CH2OH)] n (1) was synthesized by solvothermal method. The neutral [Pb2(ins)2] moieties is a tetra-coordinated dimer and holds hemidirected coordination geometry. There are secondary Pb–N interactions that give rise to 2-D polymer with holodirected geometry.A new extended 2-D lead(II) coordination polymer [Pb2(ins)2(CH3CH2OH)] n (1) (H2ins =  N-isonicotinamidosalicylaidimine) was synthesized by solvothermal method and characterized by IR, UV–vis, thermal analysis, elemental analysis and X-ray crystallography. The single-crystal X-ray data show that the neutral [Pb2(ins)2] moieties is a tetra-coordinated dimer with hemidirected coordination geometry. There are secondary Pb–N interactions that give rise to 2-D polymer with holodirected geometry. Compound 1 decomposes from 300 to 570 °C.
Keywords: Crystal structure; N-isonicotinamidosalicylaidimine; Lead(II) complex; Hemidirected; Holodirected;

Photodemetalation of silver(II) tetraphenylporphyrin by Horst Kunkely; Arnd Vogler (479-481).
The photolysis of AgIITPP (TPP = tetraphenylporphyrin) under reducing conditions leads to the release of Ag+ and formation of the free-base porphyrin H2TPP. It is suggested that this demetalation is initiated by LMCT excitation. The demetalated porphyrin undergoes secondary photoprocesses. In the presence of oxygen, the well-known formation of singlet oxygen takes place. Silver(II) porphyrins are thus able to function as sensitizers in photodynamic therapy. The released Ag+ ions could supplement or enhance the therapeutic effect.The photolysis of AgIITPP (TPP = tetraphenylporphyrin) under reducing conditions leads to the release of Ag+ and formation of the free-base porphyrin H2TPP. It is suggested that this demetalation is initiated by LMCT excitation. The demetalated porphyrin undergoes secondary photoprocesses. In the presence of oxygen, the well-known formation of singlet oxygen takes place. Silver(II) porphyrins are thus able to function as sensitizers in photodynamic therapy. The released Ag+ ions could supplement or enhance the therapeutic effect.

The reaction of o-hydroxyacetophenone–N-(2-hydroxyethyl)imine, with suitable chlorosilanes gives access to five and six-coordinate silicon complexes. The molecular structures of representative examples have been determined.The reaction of o-hydroxyacetophenone–N-(2-hydroxyethyl)imine, 1, with suitable chlorosilanes in the presence of triethylamine gives access to five and six-coordinate silicon complexes. The molecular structures of TBPY-5–34-[2-oxy-κO-acetophenone–N-(2-oxy-κO-ethyl)iminato-κN]diphenylsilane, C22H21NO2Si, 2, and OC-6–22′-bis[2-oxy-κO-acetophenone–N-(2-oxy-κO-ethyl)iminato-κN]silicon · chloroform, C20H22N2O4Si · CHCl3, 3, have been determined as representative examples.
Keywords: Hypercoordinate silicon; Complexes; Crystal structure;

Synthesis and structural characterization of a unique 3D coordination polymer [Pb(4-pya)2] n (4-pya =  trans-4-pyridylacrylate) by Yan-Jun Zhu; Zhi-Gang Ren; Wen-Hua Zhang; Yang Chen; Hong-Xi Li; Yong Zhang; Jian-Ping Lang (485-488).
A novel 3D polymeric complex 1 was prepared from reactions of Pb(OAc)2  · 3H2O with 4-Hpya under the presence of Et3N in methanol solution. The molecular structure of the title compound were characterized by elemental analysis, IR, and X-ray crystallography and their thermal and luminescent properties were studied.A novel lead(II)/4-pya coordination polymer [Pb(4-pya)2] n (1) (4-pya =  trans-4-pyridylacrylate) was synthesized and structurally characterized. Single-crystal X-ray diffraction revealed that 1 consists of a 3D network constructed from the 4-pya bridging ligand and {Pb2O2} subunits, in which each eight-coordinated Pb(II) ion adopts a dodecahedral coordination geometry. The thermal and luminescent properties of 1 in the solid state were investigated.
Keywords: trans-4-Pyridylacrylic acid; Lead; Crystal structure; Luminescence; Coordination polymer;

Synthesis, characterisation and cryomagnetic studies of a novel homonuclear Nd(III) Schiff base dimer by Joy Chakraborty; Guillaume Pilet; M. Salah El. Fallah; Joan Ribas; Samiran Mitra (489-493).
A novel homodinuclear complex [NdIII(L)(NO3)]2 has been synthesised [H2L =  N 1,N 3-bis(salicylideneimino)diethylenetriamine, a pentadentate Schiff base with N3O2 donor set] and characterised with spectroscopic and micro-analytical techniques. In the complex, the Schiff base ligand is showing an interesting chelating behaviour. Temperature dependence (2–300K) magnetic susceptibility study suggests the presence of an antiferromagnetic interaction operating via two phenoxo bridges.A novel homodinuclear complex [NdIII(L)(NO3)]2 (1) has been synthesised [H2L =  N 1,N 3- bis(salicylideneimino)diethylenetriamine, a pentadentate Schiff base with N3O2 donor set] and characterised with spectroscopic and micro-analytical techniques. Single crystal X-ray diffraction study reveals a centrosymmetric binuclear neutral entity [space group, P21/n; a  = 12.911(5); b  = 11.938(5); c  = 13.960(5) Å; Z  = 4] where Nd(III) metal centers are bridged together by two phenoxo oxygen atoms each coming from the two ligands. The most interesting fact is that two similar “salen” moieties of each ligand are behaving completely different in their coordination. In the doubly deprotonated ligand (L2−), one phenoxo oxygen is mono coordinated to the metal, whereas its immediate neighbour on the other end bridges the two Nd(III) centers. The distance between the Nd(III) centers is found to be 3.884(3) Å. Temperature dependence (2–300 K) magnetic susceptibility study suggests the presence of an antiferromagnetic interaction operating via two phenoxo bridges.

The reaction of the [ReOCl3(PPh3)2] complex with 3,5-dimethylpyrazole (3,5-Me2pzH) in acidified acetone at room temperature has been examined and a novel dinuclear oxocompound – [{ReOCl4}(μ-O){ReO(3,5-Me2pzH)4}] – has been obtained. It has been studied by IR, UV–vis spectroscopy and X-ray crystallography.The reaction of the [ReOCl3(PPh3)2] complex with 3,5-dimethylpyrazole (3,5-Me2pzH) in acidified acetone at room temperature has been examined and a novel dinuclear oxocompound – [{ReOCl4}(μ-O){ReO(3,5-Me2pzH)4}] – has been obtained. It has been studied by IR, UV–vis spectroscopy and X-ray crystallography.
Keywords: Rhenium oxocomplexes; 3,5-Dimethylpyrazole; X-ray structure; Electronic structure;

Two monomeric complexes, [Zn(trtr)2(H2O)4](NO3)2  · 2H2O (1) and [Mn(trtr)2(H2O)4](ClO4)2 (2), were obtained from the reactions of bitriazole ligand 4-[3-(1,2,4-triazolyl)-1,2,4-triazole] (trtr) with Zn(NO3)2 and Mn(ClO4)2. Two 3-D supramolecular frameworks are constructed by the hydrogen bonds and d⋯π stacking interactions. The fluorescence of 1 and 2 feature the emission peaks at 349 and 358 nm, respectively, originated from LMCT.Two monomeric complexes, [Zn(trtr)2(H2O)4](NO3)2  · 2H2O (1) and [Mn(trtr)2(H2O)4](ClO4)2 (2), were obtained from the reactions of bitriazole ligand 4-[3-(1,2,4-triazolyl)-1,2,4-triazole] (trtr) with Zn(NO3)2 and Mn(ClO4)2, respectively. A 3-D supramolecular framework of 1 is constructed by the hydrogen bonds with lattice water molecule as linkers. In 2, a 2-D supramolecular layer is formed by hydrogen bonding interactions between the monomeric assembly and ClO 4 - , and further connected into a 3-D framework by d⋯π and π⋯π stacking interactions. The coordination of the metal centers to the new born triazole ring play an important role in their fluorescent properties, which present the emission peaks at 349 nm and 358 nm, respectively, originated from LMCT.
Keywords: Mononuclear; Zn(II); Mn(II); Crystal structure; 1,2,4-Triazole; Fluorescence;

The mononuclear tetraazadiphenol macrocyclic nickel(II) complex [Ni(H2[20]-DCHDC)](ClO4)2 is obtained by reacting nickel perchlorate hexahydrate and a mixture of 2,6-diformyl-p-cresol with trans-1,2-diaminocyclohexane in methanol.The mononuclear tetraazadiphenol macrocyclic nickel(II) complex [Ni(H2[20]-DCHDC)](ClO4)2 (II) {H2[20]-DCHDC = 14,29-dimethyl-3,10,18,25-tetraazapentacyclo-[25,3,1,04,9,112,16,019,24] ditriacontane-2,10,12,14,16(32),17,27(31),28,30-decane-31,32-diol} has been synthesized by self-assembly and characterized by elemental analysis, conductance, IR and FAB-MS spectrum, and single crystal X-ray diffraction. In the mononuclear complex, the Ni(II) ion is coordinated with a square planar conformation by two phenolate groups and two iminic sites on one side of the macrocycle. The bond angles of O–Ni–O {85.37(19)°} and N–Ni–N {88.0(2)°} are smaller than 90°.
Keywords: Tetraazadiphenolic macrocycle; Macrocyclic nickel(II) complex; Mononuclear nickel(II) complex;

First example of pyrrole-2-carbaldehyde thiosemicarbazone as tridentate dianion in [Pd(η3-N 4,N 3,S-ptsc)(PPh3)] complex by Tarlok S. Lobana; Gagandeep Bawa; Alfonso Castineiras; Ray J. Butcher (506-509).
Pyrrole-2-carbaldehyde thiosemicarbazone (H2ptsc) with PdCl2(PPh3)2 forms a square planar complex, [Pd(η3- N 4,N 3,S-ptsc)(PPh3)] (1), existing as three independent molecules in the same unit cell, and H2ptsc behaves in an unusual dinegative tridentate mode.Reaction of pyrrole-2-carbaldehyde thiosemicarbazone (H2ptsc) with PdCl2(PPh3)2 in 1:1 mol ratio in presence of Et3N leads to complete dechlorination to generate square planar complex, [Pd(η3-N 4,N 3,S-ptsc)(PPh3)] (1), existing as three independent molecules in the same unit cell, and H2ptsc behaves in an unusual dinegative tridentate mode. Salicylaldehyde thiosemicarbazone (H2stsc) formed similar compound, [Pd(η3-O,N 3,S-stsc)(PPh3)] (3).
Keywords: Pyrrole-2-carbaldehyde thiosemicarbazone; Palladium(II); Triphenyl phosphine; Dechlorination;