Inorganic Chemistry Communications (v.10, #3)

Contents List (iii-x).

Synthesis, characterization and catalytic study of [N,N′-bis(3-ethoxysalicylidene)-m-xylylenediamine]oxovanadium(IV) complex by Ana Paula de Azevedo Marques; Edward Ralph Dockal; Fabiana C. Skrobot; Ieda Lucia Viana Rosa (255-261).
Structural representations of the [N,N′-bis(3-ethoxysalicylidene)-m-xylylenediamine]oxovanadium(IV) ([VO(L)]).The study of the synthesis and catalytic properties of the oxovanadium(IV) complex [N,N′-bis(3-ethoxysalicylidene)-m-xylylenediamine]oxovanadium(IV) ([VO(L)]) is the principal objective in this work. The Schiff base (L) and the its oxovanadium complex ([VO(L)]) have been characterized by elemental analysis, melting point, Fourier Transform Infra-red (FTIR), UV–Vis., 1H and 13C NMR spectroscopy. The catalytic study of the [VO(L)] in the oxidation of methyl phenyl sulfide was carried out in the homogeneous and heterogeneous systems. The catalysts were characterized by elemental analysis by flame atomic absorption spectroscopy (FAAS), IR, X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The progress of the catalytic reaction was followed by gas chromatographic analysis (GC). The oxidation of methyl phenyl sulfide after 24 h of reaction, presented for [VO(L)], [VO(L)]-alumina and [VO(L)]-Y was 50 mol%, 98 mol% and 34 mol%, respectively. In the [VO(L)]-Y system it was noted an increase in the oxidation of the methyl phenyl sulfide from 34 mol% to 92 mol% after four days. In the systems [VO(L)] and [VO(L)]-alumina the sulfide oxidation reached a maximum after 24 h of reaction. [VO(L)]-supported Y and [VO(L)]-Wessalith®P were inactive under the same reaction conditions.
Keywords: Oxovanadium(IV) complex; Schiff base ligand; Oxidation catalysts;

Polymer-supported metallocene catalysts for ethylene polymerisation: Characterisation and catalytic studies by A.S. Shearer; Y.R. de Miguel; E.A. Minich; D. Pochan; C. Jenny (262-264).
A series of polymer-supported unbridged metallocene dichloride catalysts, Cp″CpMCl2 (where Cp″ = C5Me4H and M = Ti or Zr) have been prepared. These catalysts have been characterised in detail and have shown promising activity in ethylene polymerisation under extremely mild conditions.A series of polymer-supported unbridged metallocene dichloride catalysts, Cp″CpMCl2 (where Cp″ = C5Me4H and M = Ti or Zr) have been prepared. These catalysts have been characterised in detail and have shown promising activity in ethylene polymerisation under extremely mild conditions.
Keywords: Polymer-supported; Polymerisation; Metallocene; Polyethylene; Catalysis;

The Co(II) ions are held together by two bridging hydroxides to form tetranuclear [Co43-OH)2] units, which are connected further through btc3− (H3btc = 1,2,4-benzene- tricarboxylate) ligands in a new μ7-bridging mode to give a three-dimensional porous framework. The study of magnetic properties indicated dominant antiferromagnetic coupling interactions between the adjacent Co(II) sites.A cobalt coordination polymer {[Co2(btc)(μ3-OH)(H2O)2] · H2O} n 1 (btc = 1,2,4-benzenetricarboxylate) was synthesized hydrothermally and structurally characterized by single-crystal X-ray diffraction method. In 1, the six-coordinated Co(II) ions are held together by two bridging hydroxides to form a tetranuclear [Co43-OH)2] unit, which are connected further through btc3− ligands in a new μ7-bridging mode to give a porous three dimensional framework. The study of magnetic properties indicated dominant antiferromagnetic coupling interactions between the adjacent Co(II) sites.
Keywords: Cobalt(II) complex; Hydrothermal synthesis; 1,2,4-benzenetricarboxylate; Crystal structure; Magnetic properties;

A novel photoluminescent cadmium 3D coordination polymer with 1D open channels has been successfully prepared under solvothermal conditions, which is the first example of coordination polymer composed of [Cd53-OH)23-OAc)2]6+ clusters with mixed organic linkers.A novel 3D coordination polymer, {[Cd53-OAc)22-OAc)23- OH)2(pam)2(4,4′-bpy)2] · CH3CH2OH} n (1) (H2pam = pamoic acid, HOAc = acetic acid, 4,4′-bpy = 4,4′-bipyridyl), was solvothermally synthesized and characterized by the single crystal X-ray diffraction. The title compound contains unprecedented [Cd53-OH)23-OAc)2]6+ pentanuclear building units which are linked through pam and 4,4′-bpy ligands to afford a three-dimensional structure. The infrared spectroscopy, thermal stability and photoluminescence of the complex were studied.
Keywords: Solvothermal synthesis; Crystal structure; Coordination polymer; Photoluminescent properties;

Solvothermal synthesis and structure of a neutral layered borate B3O4(OH)(C4N2H10)0.5 containing helical chains by Qinhe Pan; Wenfu Yan; Jihong Yu; Liu Yang; Minghui Bi; Jiyang Li; Ruren Xu (273-275).
A new neutral layered borate B3O4(OH)(C4N2H10)0.5 (denoted BO-CJ 38) has been solvothermally synthesized. The piperazine molecules act as organic ligand and strcuture-directing agent. The left- and right-handed helical B–O–B chains are linked together via piperazine molecules to form infinite organic–inorganic hybrid layers. The aromatic piperazine molecules may play an important role in the formation of helical inorganic chains.A new neutral layered borate B3O4(OH)(C4N2H10)0.5 (denoted BO-CJ 38) has been solvothermally synthesized. The piperazine molecules act as organic ligand and strcuture-directing agent. The left- and right-handed helical B–O–B chains are linked together via piperazine molecules to form infinite organic–inorganic hybrid layers. The aromatic piperazine molecules may play an important role in the formation of helical inorganic chains.
Keywords: Borate; Helical chain; Neutral layer; Solvothermal synthesis;

A novel bismuth ion-bridged chainlike assembly from paradodecatungstate [H2W12O42]10− anions: (NH4)7[Bi(H2W12O42)] · 20H2O by Zhen-He Xu; Xin-Long Wang; Yang-Guang Li; En-Bo Wang; Chao Qin; Yan-Ling Si (276-278).
A new polyoxotungstate (NH4)7[Bi(H2W12O42)] · 20H2O has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, TG analysis and single-crystal X-ray diffraction. The most interesting characteristic of 1 is that the paradodecatungstate [H2W12O42]10− anions are linked, for the first time, by the trivalent main group atom BiIII appeared commonly as a heteroatom, into a one-dimensional chainlike structure.A new polyoxotungstate (NH4)7[Bi(H2W12O42)] ·  20H2O has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy, TG analysis and single-crystal X-ray diffraction. The most interesting structural feature of 1 is that the paradodecatungstate [H2W12O42]10− anions are linked, for the first time, by the trivalent main group atom BiIII which appeared commonly as a heteroatom in polyoxometalate chemistry, into a one-dimensional chainlike structure.
Keywords: Polyoxometalates; Crystal structure; Bismuth; Tungstate;

Solvent-induced 1- and 2-D Cd(II) coordination polymers based on a bent polypyridyl ligand by Kai-Ju Wei; Jia Ni; Yong-Shu Xie; Qing-Liang Liu (279-282).
Two Cd(II)-tppda coordination polymers have been prepared via variations of the templating solvent molecules. The solvated complex [Cd2(tppda)(DMF)2(μ-SCN)2(SCN)2] n (1) exhibits a peculiar 1-D pseudo-helical chain, whereas the unsolvated complex [Cd2(tppda)(μ-SCN)4] n (2) features a novel 2-D metal-organic framework.Two Cd(II)-tppda (tppda =  N,N,N′,N′-tetrakis(2-pyridyl)-2,6-pyridinediamine) coordination polymers have been prepared via variations of the templating solvent. The solvated complex [Cd2(tppda)(DMF)2(μ-SCN)2(SCN)2] n (1) exhibits a 1-D pseudo-helical structure, whereas the unsolvated complex [Cd2(tppda)(μ-SCN)4] n (2) features a 2-D metal-organic framework (MOF). Both are luminescent in the solid state, with emission maxima 444 and 435 nm for 1 and 2, respectively.
Keywords: Cadmium; Coordination polymer; Metal-organic frameworks; Helical structure;

Synthesis, characterizations, and crystal structure of a novel 2D metal phosphonate: Na2[Cd2(H2O)3(O3PCH(OH)CO2)2] · 2H2O by Zhen-Gang Sun; Hui Chen; Zhong-Min Liu; Lian-Yi Cui; Yan-Yu Zhu; Yan Zhao; Jing Zhang; Wan-Sheng You; Zai-Ming Zhu (283-286).
A novel cadmium phosphonate compound Na2[Cd2(H2O)3(O3PCH(OH)CO2)2] · 2H2O (1) has been synthesized by hydrothermal reaction at 120 °C and characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. The structure of compound 1 comprises CdO6 octahedra and CdO7 pentagonal bipyramid connected by [O3PCH(OH)CO2]3− to form a 2D layered structure with a one-dimensional channel system and the charge-compensating Na+ cations being located between two adjacent layers.A novel cadmium phosphonate compound Na2[Cd2(H2O)3(O3PCH(OH)CO2)2] · 2H2O (1) has been synthesized by hydrothermal reaction at 120 °C and characterized by single-crystal X-ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. The structure of compound 1 comprises CdO6 octahedra and CdO7 pentagonal bipyramid connected by [O3PCH(OH)CO2]3− to form a 2D layered structure with a one-dimensional channel system and the charge-compensating Na+ cations being located between two adjacent layers.
Keywords: Metal phosphonates; Crystal structure; Hydrothermal synthesis; Cadmium;

Anion effect on construction of zinc(II) coordination polymer with a chelating ligand 2,2′-dipyridylamine (Hdpa): Novel heterogeneous catalytic activities by Young Min Lee; Sung Jin Hong; Hee Jin Kim; Sun Hwa Lee; Han Kwak; Cheal Kim; Sung-Jin Kim; Youngmee Kim (287-291).
The reaction of ZnSO4 with 2,2′-dipyridylamine (Hdpa) results in a coordination polymer 1 while other zinc(II) salts (bromide 2 or benzoateanions 3) produce usually monomers which can generate hydrogen-bonded polymers. The coordination polymer 1 and hydrogen-bonded polymer 2 have shown, surprisingly, unusual heterogeneous catalytic activities on transesterification reaction of esters, but the monomeric compound 3 catalyzed the reaction homogeneously..The reaction of ZnSO4 with 2,2′-dipyridylamine (Hdpa) results in a coordination polymer 1 while other zinc(II) salts (bromide 2 or benzoateanions 3) produce usually monomers which can generate hydrogen-bonded polymers. The coordination polymer 1 and hydrogen-bonded polymer 2 have shown, surprisingly, unusual heterogeneous catalytic activities on transesterification reaction of esters, but the monomeric compound 3 catalyzed the reaction homogeneously.
Keywords: Znic(II) coordination polymer; Heterogeneous catalyst; Transesterification; 2,2′-Dipyridylamine ligand;

The preparations, characterizations, structures and catalase-like activities of two homoleptic manganese(II) complexes with 4′-substituted 1,3-bis(2′-pyridylimino)isoindolines is reported. The composition and molecular structure of Mn(ind)2 complex was fully determined by IR, UV–Vis, and X-ray crystal analysis.The preparation of two homoleptic manganese(II) complexes [Mn(4′R-ind)2] [ind is the anion of 1,3-bis(2-pyridylimino)isoindoline, R = H (1), Me (2)] is described. Both complexes have been structurally characterized by UV–Vis and IR spectroscopies. Crystallographic characterization of the [Mn(ind)2] (1) complex has shown that the overall geometry around the six-coordinate manganese(II) ion is described as a slightly distorted octahedron in an N6 donor set. These complexes represent functional model systems for manganese catalases.
Keywords: Manganese; Isoindoline; Crystal structure; Catalase-like activity;

A trimetallic supramolecular complex of osmium(II) and rhodium(III) displaying MLCT transitions in the near-IR by David F. Zigler; Matthew T. Mongelli; Matthew Jeletic; Karen J. Brewer (295-298).
The light absorbing synthon [(tpy)OsCl(dpp)](PF6) has been prepared and reacted with RhCl3  · 3H2O to form the title complex [(tpy)OsCl(dpp)2RhCl2](PF6)3, tpy = 2,2′:6′,2″-terpyridine, dpp = 2,3-bis(2-pyridyl)pyrazine. Redox studies of [(tpy)OsCl(dpp)2RhCl2](PF6)3 indicate a lowest lying acceptor orbital that is Rh(dσ) based. Electronic absorption spectra of the trimetallic supramolecule and monometallic synthon show that each absorbs in the UV, visible and near-IR, with the title complex absorbing strongly throughout the range of 200–1000 nm.The mixed-metal supramolecule [{(tpy)OsCl(dpp)}2RhCl2](PF6)3 and the monometallic synthon [(tpy)OsCl(dpp)] (tpy = 2,2′:6′,2″-terpyridine, dpp = 2,3-bis(2-pyridyl)pyrazine) have been synthesized and studied by exploring redox and light absorbing properties. The complex [(tpy)OsCl(dpp)](PF6) is synthesized by the reaction of [(tpy)OsCl3] and dpp in ethylene glycol. The supramolecular complex [{(tpy)OsCl(dpp)}2RhCl2](PF6)3 is prepared by reaction of the monometallic synthon with RhCl3  · 3H2O in ethanol/water. Cyclic voltammetry shows an irreversible reduction for [{(tpy)OsCl(dpp)}2RhCl2](PF6)3 at −0.51 V (vs. Ag/AgCl) corresponding to the RhIII/II/I couple. The RhIII/II/I couple is anodic to the first dpp0/− couple, predicting a lowest lying metal-to-metal charge transfer electronic excited state. Both the monometallic and trimetallic complexes absorb in the near-IR, with [{(tpy)OsCl(dpp)}2RhCl2](PF6)3 absorbing strongly throughout the 200–1000 nm region.
Keywords: Osmium; Rhodium; NIR; Light absorber; Electrochemistry; Supramolecular; Spectroscopy;

A functionalized polyoxometalate by hexanuclear copper–amino acid coordination complexes by Haiyan An; Enbo Wang; Yangguang Li; Zhiming Zhang; Lin Xu (299-302).
Hexanuclear copper–amino acid coordination complex fragments as linkers bridge to polyoxometalates to form an unprecedented high-dimensional architecture for the first time, namely H4[Na(H2O)2][Cu6Na(gly)8(H2O)2][BW12O40]2  · 13H2O (1) (gly = glycine). Magnetic measurements show ferromagnetic interactions for compound 1.A new functionalized polyoxometalate by transition metal–amino acid coordination complexes, H4[Na(H2O)2][Cu6Na(gly)8(H2O)2][BW12O40]2  · 13H2O (1) (gly = glycine) has been synthesized and characterized by elemental analysis, IR spectroscopy, TG analysis, and single crystal X-ray diffraction. Compound 1 possesses a 3D framework, which is built up of [BW12O40]5− building blocks, hexanuclear [Cu6Na(gly)8] coordination clusters and Na+ ions. Furthermore, magnetic measurements show ferromagnetic interactions for compound 1.
Keywords: Functionalization; Polyoxometalates; Amino acids; Copper; Magnetic properties;

One-dimensional macrocyclic zinc(II) coordination polymer containing an unusual bis-monodentate oxalate bridge by Hanyoung Park; Ju Chang Kim; Alan J. Lough; Byung Min Lee (303-306).
A new zinc(II) complex, {[Zn(L1)(oxalate)] · 3.5H2O} n (1) (L  = 5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.01,18. 07,12]docosane) has been prepared and characterized by single crystal X-ray structure determination. In 1 the rigidity and steric hindrance of the macrocycle L1 causes the bridging oxalate ligand to coordinate to the zinc(II) ions in an unusual twisted bis-monodentate coordination (1,1′-bicoordination) mode.A new zinc(II) complex, {[Zn(L1)(oxalate)] · 3.5H2O} n (1) (L  = 5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.01,18.07, 12]docosane) has been prepared and characterized by single crystal X-ray structure determination. In 1 the rigidity and steric hindrance of the macrocycle L1 causes the bridging oxalate ligand to coordinate to the zinc(II) ions in an unusual twisted bis-monodentate coordination (1,1′-bicoordination) mode.
Keywords: Zinc(II) complex; Crystal structure; Coordination polymer; Tetraazamacrocycle; Oxalate ligand;

A supramolecular light absorber, [{[(bpy)2Os(dpp)]2Ru}2(dpq)](PF6)12, has been prepared. This efficient light absorber has a high molecular weight 5173 g/mol with large ε of 8.3 × 105  M−1  cm−1 at 560 nm. It possesses a lowest unoccupied molecular orbital localized on the central μ-dpq and a highest occupied molecular orbital localized on the terminal Os, providing significant spatial separation of donor and acceptor orbitals.A structurally diverse supramolecular complex, [{[(bpy)2Os(dpp)]2Ru}2(dpq)](PF6)12, has been prepared (bpy = 2,2′-bipyridine, dpp = 2,3-bis(2-pyridyl)pyrazine, and dpq = 2,3-bis(2-pyridyl)quinoxaline). The supramolecular assembly contains four light absorbing osmium metal centers coupled to two ruthenium metal centers linked by two different bridging ligands (BL) capped by bpy terminal ligands. This supramolecule possesses a lowest unoccupied molecular orbital (LUMO) localized on the central μ-dpq bridging ligand (BL) and a highest occupied molecular orbital (HOMO) localized on the terminal Os centers, providing significant spatial separation of these donor and acceptor orbitals. This hexametallic complex absorbs throughout the visible region due to overlapping singlet metal-to-ligand charge transfer (MLCT) transitions from the Os and Ru chromophores to each π-acceptor ligand. The Os based 3MLCT bands extend into the near-infrared. The light absorbing and redox properties for this hexametallic complex have been elucidated using smaller model fragments and spectroelectrochemistry.
Keywords: Supramolecular; Ruthenium complexes; Osmium complexes; Bridging ligand; Electrochemical properties; Spectroscopy; Spectroelectrochemistry;

Depending on the solvents used for crystallization, silver nitrate and the flexible dithioether-type ligand incorporating piperazine diamide [L: 1,4-bis((cyclohexylthio)acetyl)piperazine] readily formed two distinct types of 2D (1) and 3D (2) coordination polymers with identical formula [Ag2(NO3)2 L] n . The preparation and structural characterisation of 1 and 2 are reported as an example for the supramolecular isomerism.Depending on the solvents used for crystallization, silver nitrate and the flexible dithioether-type ligand incorporating piperazine diamide [L: 1,4-bis((cyclohexylthio)acetyl)piperazine] readily formed two distinct types of 2D (1) and 3D (2) coordination polymers with identical formula [Ag2(NO3)2 L] n . The preparation and structural characterisation of 1 and 2 are reported as an example for the supramolecular isomerism.
Keywords: Crystal structure; Coordination polymer; Dithioether ligand; Silver(I) complex; Supramolecular isomerism;

First use of the maleamate(−1) ligand in coordination chemistry: Dinuclear copper(II) complexes with N-donors and their interesting ‘organic’ chemistry by Katerina N. Lazarou; Iordanis Chadjistamatis; Vassilis Psycharis; Spyros P. Perlepes; Catherine P. Raptopoulou (318-323).
The reaction systems Cu(ClO4)2  · 6H2O/OOC–CH=CH–CONH2/phen or bppy, where phen = 1,10-phenanthroline and bppy = 2,6-bis(pyrazol-1-yl)pyridine, give ternary cationic dimers, whose chemical and structural identity depends on the solvent used; maleamate(−1) complexes are isolated in MeCN, whereas a novel copper(II)-assisted transformation of the maleamate(−1) ligand to monomethyl maleate(−1) has occurred in MeOH.A systematic investigation of the reactions of 3d-metal ions with the maleamate(−1) ligand (HL) in the presence of mono- , bi- or tridentate chelating N-donors has been initiated and the first results are described. Reaction schemes involving Cu(ClO4)2  · 6H2O, HL and 1,10-phenanthroline or 2,6-bis(pyrazol-1-yl)pyridine (bppy) in MeCN gave complexes [Cu2(HL)3(phen)2](ClO4) (1) and [Cu2(HL)2(bppy)2](ClO4)2 (3), respectively. The same reaction systems in MeOH afforded the new complexes [Cu2L′2(ClO4)(phen)2(MeOH)](ClO4) (2b) and [Cu2L′2(bppy)2](ClO4)2 (4) in which the maleamate(−1) ion has been transformed to the monomethyl maleate(−1) ligand L′ via a novel, metal ion-assisted process. The reaction that leads to 2b takes place through the formation of the 1D coordination polymer [Cu(ClO4)(phen)(MeOH)2] n (ClO4) n (2a), whose structure was assigned on the basis of its spectral similarity with the structurally characterized complex [Cu(ClO4)(phen)(MeCN)2] n (ClO4) n (2c). Only the carboxylate oxygen atoms of HL and L′ are coordinated to copper(II) in 1, 2b, 3 and 4.
Keywords: Copper(II)/1,10-phenanthroline complexes; Copper(II)/2,6-bis(pyrazol-1-yl)pyridine complexes; Methyl maleate(−1) complexes; Ligand transformation; Maleamate(−1) ligand;

Macrocyclic molecular square complex of zinc(II) self-assembled with a carbohydrazone ligand by Manoj Easwaran potti; Maliyeckal Ramakrishna Panicker Prathapachandra Kurup; Hoong-Kun Fun (324-328).
First example of a molecular square of carbohydrazone in the form of Zn(II) cationic macrocycle is achieved by self-assembly. Bridging mode of oxygen of bis(2-benzoylpyridine ketone) carbohydrazone (H2L) with metal centers facilitates the formation of the macrocyclic molecular square [Zn(HL)]4(BF4)4  · 10H2O. Single crystal X-ray studies and MALDI mass spectral studies confirm its existence as molecular square structure in the solid and solution phase.A novel N4O coordination mode offers carbohydrazone ligands as a building block for interesting frameworks through self-assembly. Bridging mode of oxygen of bis(2-benzoylpyridine ketone) carbohydrazone (H2L) with metal centers facilitates the formation of the macrocyclic molecular square [Zn(HL)]4(BF4)4  · 10H2O, offers wide range of applications for carbohydrazones.
Keywords: Self-assembly; Synthesis; Zinc(II); MALDI; Carbohydrazone; Crystal structure;

Adducts AgNO2:PPh3: L (1:1:1) (L = 2,2′-bipyridyl (bpy), 1,10-phenanthroline (phen), 2,9-dimethylphenanthroline (dmp)) have been synthesized and characterized by IR, far-IR, 1H and 31P NMR and a single crystal X-ray study.Adducts of the form AgNO2:PPh3: L (1:1:1) (L = 2,2′-bipyridyl (bpy), 1,10-phenanthroline (phen), 2,9-dimethylphenanthroline (dmp)) have been synthesized and characterized by analytical, spectroscopic (IR, far-IR, 1H and 31P NMR) studies, together with a single crystal X-ray study for the L = dmp adduct, for comparison with the recently reported counterpart adducts of silver(I) nitrate. While the silver(I) coordination environment is still dominated by the quasi-planar N2AgP motif (Ag–P 2.378(1), Ag–N 2.364(3), 2.392(4) Å), the interaction of the nitrite is symmetrical (Ag–O 2.512(4), 2.543(5) Å) and invasive, the PAgN2 angle sum diminished to 324.7°.
Keywords: Silver nitrite; Triphenylphosphine; Bidentate ligands; Single crystal X-ray study; NMR;

Gallium(III) phthalocyanines tetra-substituted with 3-hydroxypyridine and their water soluble quaternarized derivatives have been synthesized for the first time and the latter are non-aggregated in water over a wide concentration range.The preparation of cationic water-soluble gallium phthalocyanine derivatives are described for the first time. Peripheral and non-peripheral 3-hydroxypyridine tetrasubstituted gallium(III)phthalocyanines (5a, 6a) and their quaternarized derivatives (5b and 6b) have been synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy, electronic spectroscopy and mass spectra. The quaternarized compounds (5b and 6b) are soluble in water and not aggregated (in water and in organic solvents) within a wide concentration range. General trends are described for singlet oxygen quantum yields, fluorescence quantum yields and fluorescence lifetimes of these compounds. These complexes showed better singlet oxygen quantum yields in water than the related quarternarized porphyrazine complexes.
Keywords: Gallium; Phthalocyanine; Amphiphilic; Quaternization; Fluorescence; Singlet oxygen;

The hydrothermal assembly of CoCl2  · H2O with benzene-1, 2, 3, 4-tetracarboxylic acid (H4mpda) yielded a novel lamellar coordination polymeric complex, Co2mpda(H2O)6  · H2O (1), in which each layer presents an interesting multifold topology: both as partially overlapped helices with alternate chirality and as alternately arranged ladders and zigzag chains.The hydrothermal assembly of CoCl2  · H2O with benzene-1, 2, 3, 4-tetracarboxylic acid (H4mpda) yielded a novel lamellar coordination polymeric complex, Co2mpda(H2O)6  · H2O (1), in which each layer presents an interesting multifold topology: both as partially overlapped helices with alternate chirality and as alternately arranged ladders and zigzag chains.
Keywords: Crystal structure; Multifold motif; Magnetic property;

A novel 3D twofold interpenetrating microporous metal-organic framework containing 1D water tapes with cyclic pentamer units by Jian-Qiang Liu; Yao-Yu Wang; Ping Liu; Wei-Ping Wu; Ya-Pan Wu; Xi-Rui Zeng; Fan Zhong; Qi-Zhen Shi (343-347).
A novel three dimensional network with parallel interpenetrating topology contains 1D cavties for accommodating guest water molecules, which form 1-D hydrogen-bonded water tapes consisting of linked cyclic pentamer cluster.The self-assembly of Cu2+ ions with malate and 1,3-bis(4-pyridyl)propane (bpp) affords a 3D coordination polymer {[Cu(Hmal)(bpp) · 6H2O]} n (1) (malic acid = H3mal). The metal ions were interconnected by α- and β-carboxylate of malate produce infinite [Cu(C4H4O5)] n layers, which were further pillared by bridging ligand bpp molecules to form a 3D interpenetrating network. Of further interest, lattice water molecules form 1D infinite water tapes in 1D open cavities.
Keywords: Interpenetration; Topology; Pentamer cluster; Crystal structure; Copper(II) complex;

Two selenidostannates were prepared by solvothermal reaction. The Sn 2 Se 6 4 - anion as an bridging ligand connects two transition metal complex cations to form neutral centrosymmetric [M(tepa)]22-Sn2Se6) compounds (M =  Fe2+ and Co2+).Two new selenidostannates [M(tepa)]22-Sn2Se6) (tepa = tetraethylenepentamine, M = Fe2+ 1 and Co2+ 2) were prepared by solvothermal reaction at 157 °C. Compounds 1 and 2 are isostructural. The M2+ ion has a distorted octahedral geometry comprised of five N atoms from tepa ligands and one terminal Se atom of the Sn 2 Se 6 4 - anion. As a bridging ligand, Sn 2 Se 6 4 - anion connects two transition metal complex cations by trans terminal Se atoms to form neutral centrosymmetric [M(tepa)]22-Sn2Se6) moieties. Their thermal and optical properties were studied.
Keywords: Selenidostannates; Solvothermal synthesis; Crystal structures; Transition metal complex;

Slow crystallization of the amorphous bimetallic isopropoxides of variable composition formed on interaction of the two homometallic isopropoxides in solutions in parent alcohol yields bimetallic oxoalkoxide La2Zr3O(OPr i )16 (1) – first representative of a new molecular structure type for pentanuclear alkoxides.The amorphous bimetallic isopropoxides of variable composition LaZr n O x (OPr i )3+4n−2x , where n  = 0.5–3 formed on interaction of the two homometallic isopropoxides, La5O(O i Pr)13 and Zr(O i Pr)4( i PrOH), in solutions in parent alcohol crystallize slowly yielding a bimetallic oxoalkoxide La2Zr3O(OPr i )16 (1). In its molecule an octahedrally coordinated zirconium atom is connected via two μ3-OR and two μ-OR-groups with two lanthanum atoms of a tetrahedral [La2Zr24-O)] aggregate. This structure type has not been previously observed in the structures of pentanuclear alkoxide aggregates. The conditions leading to formation of 1 from solutions containing the homometallic alkoxides are outlined.
Keywords: Lanthanum; Zirconium; Oxoalkoxides; Crystal and molecular structure; Sol–gel; Precursor;

Fluorescence of alizarin complexone and its metal complexes by Horst Kunkely; Arnd Vogler (355-357).
Alizarin complexone (AC) in ethanol shows two fluorescence bands which originate from the lowest excited singlet before and after proton transfer. Upon addition of various metal ions (Ni2+, Zn2+, Gd3+, Th4+) to AC in ethanol the formation of well known AC complexes takes place. They are characterized by intense colours which are caused by IL (or ILCT) transitions. If low-energy LF states (Ni2+) are absent (Zn2+, Gd3+, Th4+) these complexes show a weak fluorescence. Even in the case of Gd and Th a heavy-atom effect is not apparent and fluorescence quenching is not observed. Moreover, AC complexes are not phosphorescent under any conditions.Alizarin complexone (AC) in ethanol shows two fluorescence bands which originate from the lowest excited singlet before and after proton transfer. Upon addition of various metal ions (Ni2+, Zn2+, Gd3+, Th4+) to AC in ethanol the formation of well known AC complexes takes place. They are characterized by intense colours which are caused by IL (or ILCT) transitions. If low-energy LF states (Ni2+) are absent (Zn2+, Gd3+, Th4+) these complexes show a weak fluorescence. Even in the case of Gd and Th a heavy-atom effect is not apparent and fluorescence quenching is not observed. Moreover, AC complexes are not phosphorescent under any conditions.
Keywords: Electronic spectra; Fluorescence; Alizarin; Metal complexes;

The solvothermal reaction of [ Et 4 N ] 4 [ W 4 Cu 4 S 12 O 4 ] , CuI, 4,4′-bipy and 4-nitoraniline with a mole of 1:4:2:2 resulted in the formation of a novel 2D cluster-containing compound { [ WOS 3 Cu 3 ( 4 , 4 ′ -bipy ) 3 ] [ I ] } n , which exhibits Borromean links with { WOS 3 Cu 3 } cluster units as connecting knots and 4,4′-bipy ligands as spacers.The solvothermal reaction of [ Et 4 N ] 4 [ W 4 Cu 4 S 12 O 4 ] , CuI, 4,4′-bipy and 4-nitoraniline with a molar ratio of 1:4:2:2 resulted in the formation of a novel 2D cluster-containing compound { [ WOS 3 Cu 3 ( 4 , 4 ′ -bipy ) 3 ] [ I ] } n , which exhibits Borromean links with { WOS 3 Cu 3 } cluster units as connecting knots and 4,4′-bipy ligands as spacers.
Keywords: Crystal structure; Metal cluster; Brorrmean links;

Unusual metal-organic frameworks built from 2D layers through Cl⋯Cl contacts and hydrogen bonds by Hai-Bin Zhu; Zhao-Lian Chu; Da-Hua Hu; Wei Huang; Shao-Hua Gou (362-366).
Reactions of dtcp(2,6-di(1,2,4-triazol-1-ylmethyl)-4-chlorophenol) with Zn(NO3)2 and MnCl2, respectively, followed by treatment of excess NH4SCN, afford unusual metal-organic frameworks [Zn(dtcp)2](SCN)2 (1) and [Mn(dtcp)2](SCN)2 (2), both of which are built from 2D layers through hydrogen bonds (C–H⋯N and C–H⋯S) and Cl⋯Cl contacts.Unusual metal-organic frameworks [M(dtcp)2](SCN)2 [M = Zn, Mn; dtcp = 2,6-di(1,2,4-triazol-1-ylmethyl)-4-chlorophenol] are composed of 2D rhombus-type grid networks associated mutually by remarkable Cl⋯Cl contacts and hydrogen bonds (C–H⋯N and C–H⋯S). Both thermogravimetric analysis and photoluminescence measurements are performed as well to characterize these supramolecular frameworks.
Keywords: MOFs; Hydrogen bond; 1, 2, 4-Triazole; Chlorine;

[Cr(3-HNA)(en)2]Cl · H2O · CH3OH is synthesized. The kinetics of transfer of Cr3+ from the title compound to the low-molecular-mass chelator EDTA and to the iron-binding protein apoovotransferrin (apoOTf) were followed by a combination of UV–Visible (UV–Vis) and fluorescence spectra in 0.01 M Hepes at pH 7.4.The reaction of chromium(III) chloride, 3-hydroxy-2-naphthoic acid (3-HNA) and ethylenediamine (en) led to the formation of complex [Cr(3-HNA)(en)2]Cl · H2O · CH3OH, Bis(ethylenediamine-κ2 N,N′)(3-hydroxy-2-naphthoic acid-κ2 O,O′) chromium(III) monochloride monohydrate monomethanol. The kinetics of transfer of Cr(III) from the title compound to the low-molecular-mass chelator EDTA and to the iron-binding protein apoovotransferrin (apoOTf) were carried out by means of UV–Visible (UV–Vis) and fluorescence spectra in 0.01 M Hepes at pH 7.4. The second-order rate constants were calculated, respectively. The results show that Cr(III) can be transferred from the complex to apoovotransferrin.
Keywords: Chromium(III); Crystal structure; Apoovotransferrin; Kinetics;

Synthesis and crystal structures of mono-, bis- as well as tris-mercurated complexes with ferrocenylazines by Xin-Qi Hao; Jun-Fang Gong; Wen-Tao Song; Yang-Jie Wu; Mao-Ping Song (371-375).
The mono-(cyclomercurated) complex (2) and bis-(cyclomercurated) complexes (3) as well as the first example of a tris-mercurated ferrocenylimine (4) have been conveniently prepared from the reaction of ferrocenylazines (1) with Hg(OAc)2 and subsequent treatment with LiCl. All the new compounds were characterized by elemental analysis, 1H NMR, IR spectra and X-ray single crystal analysis.The mono-(cyclomercurated) complex (2) and bis-(cyclomercurated) complexes (3) as well as the first example of a tris-mercurated ferrocenylimine (4) have been conveniently prepared from the reaction of ferrocenylazines (1) with Hg(OAc)2 and subsequent treatment with LiCl. All the new compounds were characterized by elemental analysis, 1H NMR and IR spectra. X-ray single crystal analysis confirms that complex 2 exists as a tetramer in the crystal due to intermolecular bridged Cl–Hg bonds and weak intermolecular N–Hg coordination. While 3b and 4 have a one-dimensional chain structure formed by intermolecular bridged Cl–Hg bonds and CH(Cp)⋯Cl hydrogen bonds.
Keywords: Ferrocenylazine; Mercurated; Crystal structure; Synthesis;

1D helical ZnII metal–organic polymers: Syntheses, structures and fluorescent properties by Bo Xiao; Hongwei Hou; Yaoting Fan; Mingsheng Tang (376-380).
Hydrothermal reactions of 1,1′-(1,5-pentanediyl)bis-1H-benzimidazole (pbbm) with ZnCl2 afford two 1D helical metal–organic polymers {[ZnCl2(pbbm)] · (H2O)1/8} n (1) and {[Zn(pbbm)2] · Cl2  · (H2O)1/2} n (2). Polymer 1 has a 1D single helical chain structure, while 2 possesses a 1D cationic double helical chain framework. Both of them display strong fluorescent emissions in the solid state at room temperature, which could originate from a ligand-to-ligand charge-transfer (LLCT) transition, as confirmed by the molecular orbital (MO) calculations.Hydrothermal reactions of 1,1′-(1,5-pentanediyl)bis-1H-benzimidazole (pbbm) with ZnCl2 afford two 1D helical metal–organic polymers {[ZnCl2(pbbm)] · (H2O)1/8} n (1) and {[Zn(pbbm)2] · Cl2  · (H2O)1/2} n (2). Polymer 1 features a 1D single helical architecture, whereas 2 possesses a 1D cationic double helical chain framework. Photoluminescence investigations reveal that both of them display strong emissions in the solid state at room temperature, which could originate from a ligand-to-ligand charge-transfer (LLCT) transition, as confirmed by the molecular orbital (MO) calculations.
Keywords: Zinc; Metal–organic polymer; Crystal structure; Helix; Fluorescence; MO calculation;

Two lanthanide coordination polymers, [{Ln2(bpdc)3(phen)2(H2O)2} · (H2O)6] n (Ln = Dy (1); Ho (2)) were obtained from 2,2′-bipyridine-3,3′-dicarboxylic acid (H2bpdc), 1,10-phenanthroline (phen) and corresponding lanthanide oxides by hydrothermal synthesis. Single-crystal X-ray diffraction shows that 12 are all one-dimensional zigzag chain structures and extend to two-dimensional networks through π–π interactions and hydrogen bonds. Photoluminescence measurement indicates that 1 is a strong yellow emitterTwo lanthanide coordination polymers, [{Ln2(bpdc)3(phen)2(H2O)2} · (H2O)6] n (Ln = Dy (1); Ho (2)) were obtained from 2,2′-bipyridine-3,3′-dicarboxylic acid (H2bpdc), 1,10-phenanthroline (phen) and corresponding lanthanide oxides by hydrothermal synthesis. Polymers 12 are found to be isostructural. Single-crystal X-ray diffraction shows that 1–2 are all one-dimensional zigzag chain structures and extend to two-dimensional networks through π–π interactions and hydrogen bonds. Thermogravimetric analysis of 12 displays a considerable thermal stability. The variable-temperature magnetic susceptibility of both compounds was measured. Photoluminescence measurement indicates that 1 is a strong yellow emitter.
Keywords: Lanthanide; Coordination polymer; Hydrothermal synthesis; X-ray diffraction;