Inorganic Chemistry Communications (v.12, #2)

Contents List (iii-xii).

A novel polyoxometalate cluster decorated with the directly coordinated organonitrogen ligands: [As(phen)]2[As2Mo2O14] by Yunan Zhang; Baibin Zhou; Zhanhua Su; Zhifeng Zhao; Chunxiang Li (65-68).
A novel 1D chained organic–inorganic molybdenum arsenate compound decorated with the directly coordinated organonitrogen ligands: [As(phen)]2[As2Mo2O14] is reported for the first time. Furthermore, a two-dimensional supermolecule layer structure is formed by π–π stacking interactions of the phen groups between adjacent chains.A novel organic–inorganic molybdenum arsenate compound with chain structure, [As(phen)]2[As2Mo2O14] (phen = 1,10′-phenanthroline) 1, has been synthesized by the hydrothermal reaction and structurally characterized. Compound 1 represents the first example which contains an unusual 1D {As/Mo/O} chain with the phen ligands directly coordinated to the As atoms. Furthermore, a two-dimensional supramolecule layer is formed by π–π stacking interactions of the phen groups between adjacent chains. The electrochemical behavior of 1 modified CPE (1-CPE) has been also studied.
Keywords: Polyoxometalates; Molybdenum arsenate; Directly coordinated organic ligands; Electrochemistry;

A novel polyoxotungstate cluster [Fe6Ge3W24O94(H2O)2]14− (1a) has been hydrothermally synthesized and structurally characterized by IR, TGA and single-crystal X-ray diffraction. The polyoxoanion skeleton of 1 is composed of two tri-FeIII substituted B-α-(Fe3GeW9O40) Keggin units connected by an unique hexavacant GeW6O26 Keggin fragment, leading to a banana-shaped structure with the idealized C 2 V symmetry.A novel polyoxotungstate cluster (H2en)2.5H9[Fe6Ge3W24O94(H2O)2] · 14H2O (1) (en = ethylenediamine) has been hydrothermally synthesized and structurally characterized by IR, TGA and single-crystal X-ray diffraction. The polyoxoanion skeleton of 1 is composed of two tri-FeIII substituted B-α-(Fe3GeW9O40) Keggin units connected by an unique hexavacant GeW6O26 Keggin fragment, leading to the first Fe(III)-containing banana-shaped tungstogermanate. Magnetic measurements of 1 reveal that the exchange interactions within the trimetal clusters are antiferromagnetic.
Keywords: Polyoxometalate; Hydrothermal synthesis; Magnetism; Keggin structure;

A novel cadmium(II) coordination polymer, [Cd2(pzdc)2(4,4′-bpy)2] · 4H2O (1) has been synthesized by hydrothermal reaction of Cd(OAC)2, H2pzdc and 4,4′-bpy. 1 constructed from dinuclear building blocks has a three-dimensional (3-D) structure with rob topology. Fluorescent measurement of 1 exhibits strong blue-green emission in the solid state at room temperature, and its framework possess remarkable thermal stability.A novel cadmium(II) coordination polymer, [Cd2(pzdc)2(4,4′-bpy)2]·4H2O (1) (H2pzdc = pyrazine-2,3-dicarboxylic acid; 4,4′-bpy = 4,4′-bipyridine), has been synthesized by hydrothermal reaction of Cd(OAC)2, H2pzdc and 4,4′-bpy. Single-crystal X-ray diffraction analysis reveals that 1 constructed from dinuclear building blocks has a three-dimensional (3-D) structure with rob topology. Fluorescent measurement of 1 exhibits strong blue-green emission in the solid state at room temperature, and its framework possess remarkable thermal stability.
Keywords: Coordination polymer; Cadmium(II); Dinuclear building block; Photoluminescence;

Two-dimensional organic–inorganic hybrid materials based on β-octamolybdate units linked by [{Cu(imi)(phen)}2Cl]3+ and K+ bridges by Haijuan Jin; Baibin Zhou; Chunmei Wang; Zhanhua Su; Zhifeng Zhao; Yunan Zhang; Chuncheng Zhu (76-78).
A novel 2D hybrid framework with the β- [ Mo 8 O 26 ] 4 - building blocks linked via [ Cu ( imi ) ( 1 , 10 -phen ) 2 Cl ] 3 + and K+ bridges: K[{Cu(imi)(1,10-phen)}2Cl][Mo8O26] is reported for the first time. Furthermore, the Cu center of the [ Cu ( imi ) ( 1 , 10 -phen ) 2 Cl ] 3 + cation is five-coordinated to furnish a slightly deformed squarepyramidal geometry.A new organic–inorganic hybrid material, formulated as K[{Cu(imi)(phen)}2Cl][Mo8O26] (1) (imi = imidazole, phen = 1,10-phenanthroline), has been synthesized under hydrothermal conditions and structurally characterized by elemental analysis, IR spectra, thermal analysis and single-crystal X-ray diffraction. Compound 1 consisted of β - [ Mo 8 O 26 ] 4 - cluster, dinuclear copper complex [ Cu ( imi ) ( phen ) 2 Cl ] 3 + and K+ ion, in which the β-octaolybdate building block is linked by the coordination bridge [ Cu ( imi ) ( phen ) 2 Cl ] 3 + and the inorganic bridge K+ into a 2D organic-inorganic framework through M–O–M′ bonds (M = Mo, M′ = Cu, K). The electrochemical behavior of compound 1 has been studied in detail based on a solid bulk-modified carbon paste electrode of compound 1 (1-CPE).
Keywords: Two-dimensional; β-Octamolybdate; Hydrothermal synthesis; Electrochemical property; Mixed ligands;

Synthesis, characterization and spectroscopic studies of two new schiff-base bithienyl pendant-armed 15-crown-5 molecular probes by Bruno Pedras; Luz Fernandes; Elisabete Oliveira; Laura Rodríguez; M. Manuela M. Raposo; José Luis Capelo; Carlos Lodeiro (79-85).
Two new ligands provided with a 15-crown-5 as receptor unit and bithiophen unit as emissive probe have been synthesized and characterized in order to evaluate the coordination capabilities and their sensor effect. Solid metal complexes of Ni(II), Pd(II), Hg(II) and Na(I) have been synthesized using both macrocyclic compounds, and have been studied in solution in the presence of the same metal ions. The sensorial effect has been studied using absorption, emission and MALDI-TOF-MS spectroscopies.Two new ligands provided with a 15-crown-5 as a receptor unit and bithiophen unit as an emissive probe have been synthesized and characterized in order to evaluate the coordination capabilities and their sensor effect. Ligand L1 presents an aromatic crown ether moiety that is directly linked to the imine-2,2′-bithiophene π–conjugated system, and ligand L2 is constituted by an aliphatic crown ether moiety that is linked to the same imine-2,2′-bithiophene system through a methylene unit. Solid metal complexes of Ni(II), Pd(II), Hg(II) and Na(I) have been synthesized using both macrocyclic compounds, and have been studied in solution in the presence of the same metal ions. All solid compounds have been characterized by common analytical and spectroscopic techniques. The sensorial effect has been studied using absorption, emission and MALDI-TOF-MS spectroscopies.
Keywords: Nickel(II); Palladium(II); Mercury(II); Sodium(I); Bithiophene; Crown ether; Schiff base; Luminescence;

A novel uranyl complex UO2(tci)(C3H5N2) · H2O: Synthesis, crystal structure and characterization by Lingling Liang; Yige Cai; Ng Seik Weng; Ronglan Zhang; Jianshe Zhao; Jifeng Wang; Hongling Wu (86-88).
As a complicated complex, UO2(tci)(C3H5N2) · H2O is prepared by uranyl ion and tciH3 which contains three nitrogen atoms, three carbonyl groups and three propionic acid groups. Each uranium atom is located in a hexagonal bipyramidal environment, surrounded by eight oxygen atoms, six of which are in the equatorial plane and are from three carboxyl groups in bidentate coordination to the UO 2 2 + center. The remaining two oxygen atoms are terminal and occupy the two axial positions to complete the coordination sphere of the U(VI) center.Reaction of uranium oxynitrate hexahydrate with tris(2-carboxyethyl)isocyanurate (tciH3) in acidic aqueous solution (pH ∼4–5) yields the compound UO2(tci)(C3H5N2) · H2O. X-ray diffraction shows that the uranyl ion is in a hexagonal bipyramid structure. Uranium ion in the complex is found to be ligated with three chelating COO groups at the equatorial plane, two oxygen atoms linking to uranium atom formed the vertical axis. The complex has the layered topology structure in the space. The thermal analysis verifies the component and the structure of the complex.
Keywords: Hydrothermal reaction; Uranium complex; Crystal structure;

Multifunctional zinc(II) urocanate with rare fivefold interpenetrating diamondoid network by Xia Feng; Yi-Hang Wen; You-Zhao Lan; Yun-Long Feng; Chun-Yu Pan; Yuan-Gen Yao (89-91).
A novel zinc complex with rare 3D porous fivefold interpenetrating diamondoid network has been hydrothermally synthesized It has a SHG efficiency and strong fluorescent emission bands in the solid state.A novel zinc complex with rare 3D porous fivefold interpenetrating diamondoid network, {[Zn(L)2]H2O} n (HL = urocanic acid) (1), has been hydrothermally synthesized and characterized. It has notable non-linear optical (NLO) effect about three times as large as that of KDP and displays green fluorescent emission in the solid state.
Keywords: Hydrothermal synthesis; Diamondiod network; 1D open channel; Non-linear optical effect; Photoluminescent property; Theory calculation;

Initial use of 1-hydroxybenzotriazole in the chemistry of group 12 metals: An 1D zinc(II) coordination polymer and a mononuclear cadmium(II) complex containing the deprotonated ligand in a novel monodentate ligation mode by Athanassios D. Katsenis; Nikolia Lalioti; Vlasoula Bekiari; Panagiotis Lianos; Catherine P. Raptopoulou; Aris Terzis; Spyros P. Perlepes; Giannis S. Papaefstathiou (92-96).
The use of 1-hydroxybenzotriazole in the chemistry of group 12 metals afforded an 1D zinc(II) coordination polymer and a mononuclear cadmium(II) complex that forms undulating hydrogen bonded layers where lattice water molecules form 1D hydrogen bonded tapes, comprising 4- and 6-membered rings and bridge them to the third dimension.The chemistry of 1-hydroxybenzotriazole (btaOH) with the group 12 metal ions Zn(II) and Cd(II) resulted in the 1D coordination polymer [Zn(btaO)2] n (1) and the mononuclear complex [Cd(btaO)2(H2O)4] · 3H2O (2  · 3H2O), respectively. Polymer 1 forms double-stranded chains which are further supported by weak C–H⋯O hydrogen bonds resulting in a pcu (primitive cubic) rod packing. The mononuclear complexes of 2 form undulating hydrogen bonded layers while the lattice water molecules form 1D hydrogen bonded tapes, comprising 4- and 6-membered rings, within the layers and bridge them to the third dimension. The thermal and optical properties of both compounds are presented. IR data are discussed in terms of the chemical composition of the compounds and the coordination mode of btaO.
Keywords: Coordination polymer; Cadmium; Hydrogen bond; 1-Hydroxybenzotriazole; Zinc;

Thermal dehydration reactions of Y(TFA)3(H2O)3 (A) were investigated to obtain a better anhydrous precursor for various applications in materials science and catalysis. A partially dehydrated [Y(μ-TFA)3(THF)(H2O)] · THF (1), a partially hydrolyzed [Y43-OH)4(μ-TFA)6(TFA)2(THF)3(DMSO)(H2O)] · 6THF (2) and an anhydrous Y(TFA)3(THF)2 (3) were obtained under different thermal conditions and were characterized by elemental analyses, FT-IR and 1H NMR spectroscopy, as well as thermo-gravimetric analysis. In addition, single crystal X-ray structures are reported for 1 and 2.In order to obtain a better anhydrous precursor for various applications in materials science and catalysis, thermal dehydration reactions of Y(TFA)3(H2O)3 (TFA = trifluoroacetate) (A) were investigated. Thermal treatment of A at different temperatures under vacuum (5 × 10−2  mm) for several hours failed to give totally anhydrous yttrium trifluoroacetate (as indicated by IR). Two different complexes, a partially dehydrated [Y(μ,η11-TFA)3(THF)(H2O)]1∞·THF (1) and a partially hydrolyzed [Y43-OH)4(μ,η11-TFA)61-TFA)(η2-TFA)(THF)3(DMSO)(H2O)] · 6THF (2), were obtained with good and moderate yield, respectively, by crystallization of two different thermally treated batches of A from THF (or THF + DMSO) at room temperature. More efficient dehydration of A could be achieved at 200 °C in a furnace, the obtained anhydrous yttrium tris-trifluoroacetate giving Y(TFA)3(THF)2 (3) on crystallization from THF. All the products were characterized by elemental analyses, FT-IR and 1H NMR spectroscopy as well as thermo-gravimetric analysis. In addition, single crystal X-ray structures are reported for 1 and 2, which show either a terminal (η1 and η2) or bridging (μ,η11) bonding behavior of the TFA ligand.
Keywords: Yttrium; Trifluoroacetate; Precursor; Dehydration; X-ray structure;

Novel heterometallic Cu(II)/Cr(III) complex with unique open-chain N-ligand produced in conditions of direct template synthesis by Vitalina M. Nikitina; Oksana V. Nesterova; Vladimir N. Kokozay; Viktoriya V. Dyakonenko; Oleg V. Shishkin; Julia Jezierska (101-104).
New Cu(II)/Cr(III) complex, that contains unique open-chain Schiff-base ligand trenac (N-(2-{[(1E)-3-amino-1,3-dimethylbutylidene]amino}ethyl)-N-(2-aminoethyl)ethane-1,2-diamine), has been prepared using one-pot self-assembly reaction of copper powder, Reineckes salt, tren and acetone in dmso. The structural features, spectroscopic and magnetic properties are reported.The one-pot self-assembly reaction of copper powder, Reineckes salt, acetone and tris(2-aminoethyl)amine (tren) in dmso affords to obtain a heterometallic compound [Cu(trenac)][Cr(NCS)4(NH3)2](NCS) · 6dmso with novel Schiff-base ligand N-(2-{[(1E)-3-amino-1,3-dimethylbutylidene]amino}ethyl)-N-(2-aminoethyl)ethane-1,2-diamine (trenac). The ligand trenac is generated by metal-directed condensation of tren, acetone and ammonia, formed during the synthetic procedure. X-ray structural investigations showed that the complex consists of [Cu(trenac)]2+ cations, anions of the Reineckes salt [Cr(NCS)4(NH3)2], uncoordinated thiocyanate groups and dmso molecules, which are held together by electrostatic forces and hydrogen-bonded interactions. The compound was characterized by EPR spectroscopic and magnetic susceptibility measurements.
Keywords: Schiff-base ligand; Reineckes anion; Copper(II);

Uncomplicated, highly symmetric 3D-nets serve as ‘‘MOF blue-prints” and the discovery of new such nets enhances the scope of MOF synthesis and applications. We report here a new uniform 3D-net based on five-connected nodes with topology 610-loh, discovered in a bariumoxalate coordination polymer investigated by X-ray diffraction at low temperature.The structures of three compounds from the system Ba(C2O4) m (HC2O4) n (H2C2O4) p (H2O) q have been structurally reinvestigated by low-temperature X-ray diffraction. Ba(C2O4)(H2O)2, 1, Ba(C2O4)(H2C2O4)(H2O)2, 2, and Ba(C2O4)0.5(HC2O4)(H2O), 3. The compounds are composed of three-dimensional coordination network structures with bridging oxalates and water molecules. Compound 1 is binodal, four and five connected with topology (4462)(4466)-tcs; 2 contains the common 66-dia; net and 3 displays the new uniform network topology 610-loh. Together with the recently reported 610-ghw and 610-rld-z nets, and the 610-fnu net, the loh net forms a subclass of five-connected 610-nets based on the distorted trigonal bipyramidal coordination.
Keywords: X-ray diffraction; Coordination polymers; Network analysis; 3D-nets; MOF;

Reaction of Np(V) glycolate with 2,2′-bipyridyl led to the formation of [NpO2(C2O3H3)(Bipy)] · 2.5H2O complex as determined using X-ray single crystal diffractometry. The crystal structure is confirmed by IR and UV–vis spectroscopic data.As a result of Np(V) glycolate reaction with 2,2′-bipyridyl, the novel coordination polymer [NpO2(C2O3H3)(Bipy)] · 2.5H2O was formed. The structure consists of infinite chains of [NpO2(C2O3H3)(Bipy)] and water molecules. The crystal structure is confirmed by IR and UV–vis spectroscopic data. This complex is the first example of An glycolate with neutral molecular ligand.
Keywords: Neptunium; Coordination polymer; Crystal structure; Electronic spectrum; IR spectrum;

A new supramolecular compound based on MnIII-Schiff-base and β-octamolybdate by Yunwu Li; Yonghui Wang; Yangguang Li; Enbo Wang (112-115).
A novel layered supramolecular compound [N(CH3)4]2[Mn(Salen)(DMF)2]2[β-Mo8O26] · 2DMF (1), has been synthesized and structurally characterized. Compound 1 represents a new and rare example constructed by β-octamolybdate isopolyoxoanions and MnIII-salen Schiff-base building blocks. Moreover, the reaction contains the unusual N ( CH 3 ) 4 + cations generated in situ from the decomposition and alkylation reaction of DMF precursors.A novel layered supramolecular compound [N(CH3)4]2[Mn(Salen)(DMF)2]2[β-Mo8O26] · 2DMF (1) (H2salen =  N,N′-ethylenebis(salicylideneimine)) has been synthesized and characterized by elemental analysis, IR, TG, UV and single-crystal X-ray diffraction analysis. Compound 1 represents a new and rare example constructed by MnIII-salen Schiff-base building blocks and β-octamolybdate isopolyoxoanions. Moreover, the reaction contains the unusual N ( CH 3 ) 4 + cations generated in situ from the decomposition and alkylation reaction of DMF precursors. The electrochemical of cyclic voltammetry and electrocatalytic properties of 1 have been well investigated.
Keywords: Supramolecular; MnIII-Schiff-base; β-Octamolybdate; In situ reaction;

A new coumarin-based chemosensor for Fe3+ in water by Junna Yao; Wei Dou; Wenwu Qin; Weisheng Liu (116-118).
A new coumarin derivative bearing three hydroxyls effectively senses Fe3+.A new coumarin derivative L was synthesized, and the binding property of the L towards metal ions was examined through the changes in fluorescence intensity. L exhibited high selectivity for Fe3+ in HEPES aqueous buffer (pH 7.2), and the selectivity was not affected by the presence of representative alkali metals, alkali earth metals and other transition-metal salts. The binding mode was investigated by UV spectra, ESI-MS and IR data.
Keywords: Fe3+; Sensor; Fluorescence quenching; Coumarin derivatives;

Solvothermal syntheses, characterizations and properties of two new NiII-PMIDA phosphonates by Kui-Rong Ma; Jia-Ning Xu; De-Kuan Ning; Jing Shi; Dao-Jun Zhang; Yong Fan; Tian-Yong Song (119-121).
Two phosphonates (NH4)2[Ni(PMIDA)(H2O)] (1), (H3O)8[Ni4O2(HPMIDA)4(H2O)2] (2), between Ni(II) ion and N-(phosphonomethyl)iminodiacetic acid (H4PMIDA), were isolated from solvothermal reaction. Two compounds are characterized by single-crystal and powder X-ray diffraction, infrared spectroscopy, thermal analysis, elemental analysis, fluorescent spectroscopy and magnetic measurements. Results indicate that there is weak antiferromagnetic interaction in compound 1, however, spin-canting antiferromagnetic exchange between Ni(II) centers in compound 2.Two new nickel(II) phosphonates (H4PMIDA =  N-(phosphonomethyl)iminodiacetic acid, H4L), one-dimensional zigzag chain (NH4)2[Ni(PMIDA)(H2O)] (1) and tetramer (H3O)8[Ni4O2(HPMIDA)4(H2O)2] (2), have been solvothermally synthesized and characterized by elemental analyses, IR, TGA and X-ray single-crystal diffraction, and their magnetic and fluorescent properties are also reported.Compound 1 is the first chain phosphonate linked by carboxyl group in antianti mode based on Ni(II) and H4PMIDA ligand, and compound 2 with tetranuclear units is the first example of showing the spin-canting antiferromagnetic coupling between Ni(II) centers.
Keywords: Ni(II) phosphonate; Solvothermal; Magnetism; Fluorescence;

The terminal binding of base mismatched oligonucleotide d(CCGAATGAGG)2 by [Co(phen)2(DPQ)]Cl3 by Huili Chen; Chunjiao Dou; Yanbo Wu; Xiaoli Xi; Wei Gao; Pin Yang (122-124).
The terminal binding of [Co(phen)2(DPQ)]Cl3 to d(CCGAATGAGG)2 containing two pairs of sheared G:A mispair was proved by 2D-NMR.The binding of the complex [Co(phen)2(DPQ)]Cl3 to the decanucleotide d(CCGAATGAGG)2 containing two pairs of sheared G:A mispairs was studied by 2D-NMR. There appear many 1H NOE cross-peaks from the complex to the oligonucleotide. The results indicate that the complex, with DPQ, intercalates into the oligonucleotide via its terminal base pairs from the minor groove, which further proved our previous conclusion.
Keywords: Mismatched DNA; Cobalt complex; Intercalation; NMR;

Synthesis and characterisation of new iron(III) compounds containing the first examples of pendant-armed alcohols of cyclen by Abd-Alhakeem H. Abu-Nawwas; Christopher A. Muryn; Mohammad A. Malik (125-127).
The synthesis and structures of number of new multi-metallic compounds of iron(III) formed by the reactions of (Et4N)2[Fe2OCl6] with pendant-arm alcohols(1,4-H2DHED, H3TRED, H4THED) and carboxylic acids(1,4-H2DO2A) based upon cyclen in methanolic solution are reported.The synthesis and structures of number of new multi-metallic compounds of iron(III) formed by the reactions of (Et4N)2[Fe2OCl6] with pendant-arm alcohols(1,4-H2DHED, H3TRED, H4THED) and carboxylic acids(1,4-H2DO2A) based upon cyclen in methanolic solution are reported.
Keywords: Ethylalcohol-cyclen; Macrocyclic ligands; Iron(III) complex; Crystal structure; Defective double cubane;

Reactions of phenylbis(2-pyridyl)phosphine with oxorhenium(v) complexes by Sonia A. Saucedo Anaya; Adelheid Hagenbach; Ulrich Abram (128-130).
[ReOCl3(PPh3)2] reacts with phenylbis(2-pyridyl)phosphine (PPhpy2) in boiling THF under the formation of the rhenium(III) compound [ReCl3(PPh3)(OPPhpy2-O,N)]. Reduction of the metal is avoided by milder reaction conditions, and an asymmetric, oxo-bridged rhenium(V) dimer of the composition (NBu4)[Re2O2Cl5(μ-PPhpy2-P,N,N′)(μ-O)] is obtained from the reaction of PPhpy2 and (NBu4)[ReOCl4] in THF at room temperature.[ReOCl3(PPh3)2] reacts with phenylbis(2-pyridyl)phosphine (PPhpy2) in boiling THF under the formation of the rhenium(III) compound [ReCl3(PPh3)(OPPhpy2-O,N)]. Reduction of the metal can be avoided by milder reaction conditions, and an asymmetric, oxo-bridged rhenium(V) dimer of the composition (NBu4)[Re2O2Cl5(μ-PPhpy2-P,N,N′)(μ-O)] is obtained from the reaction of PPhpy2 and (NBu4)[ReOCl4] in THF at room temperature. The products have been characterized spectroscopically and by X-ray structure analyses.
Keywords: Rhenium; Oxo complexes; Pyridylphosphines; X-ray structure;

Diastereoselectivity and molecular recognition of mercury(II) ions by Anna Reynal; Josep Albero; Anton Vidal-Ferran; Emilio Palomares (131-134).
Colorimetric mercury sensing using two different diastereoisomers show different selectivity.Two diastereoisomers of a new heteroleptic ruthenium cis-dithiocyanate dicarboxy-bipyridyl phenanthrolyl complex have been synthesized and characterized. This type of complexes can selectively bind mercury ions through the sulphur atoms on the thiocyanate groups. The properties of these complexes as chemosensor towards Hg2+ in solution and anchored onto a mesoporous Al2O3 film have been studied and analysed. A different level of sensitivity versus mercury ions in aqueous solutions was observed for each stereoisomer.
Keywords: Colorimetric; Ruthenium complex; Mercury; Chemosensor; Diastereoselective;

New o-carboranyl-containing capping agents for d-metal tris-dioximates and first bis-C-carboranylboron-capped iron(II) clathrochelates: Synthesis and X-ray structure by Sergey Y. Erdyakov; Yan Z. Voloshin; Irina G. Makarenko; Ekaterina G. Lebed; Tamara V. Potapova; Anatolii V. Ignatenko; Anna V. Vologzhanina; Mikhail E. Gurskii; Yurii N. Bubnov (135-139).
The first use of derivatives of C-carboranylboronic acids for capping of the clathrochelate complexes is reported. The initial carboranyl-containing boron dichlorides were prepared via metallation of 1-isopropyl- and 1-ethyl-o-carborane with n-butyllithium followed by borylation with boron trichloride. Their further template condensation with nonmacrocyclic iron(II) tris-nioximate afforded the C-carboranylboron-capped alicyclic iron(II) clathrochelates.The first use of C-carboranylboronic acid derivatives for capping of the clathrochelate complexes is reported. The initial carboranyl-containing boron dichlorides were prepared via metallation of 1-isopropyl- and 1-ethyl-o-carborane with n-butyllithium followed by borylation with boron trichloride. Their further template condensation with nonmacrocyclic iron(II) tris-nioximate afforded the C-carboranylboron-capped alicyclic iron(II) clathrochelates.
Keywords: Macrocycles; Iron complexes; Clathrochelates; Carborane; Organic boron compounds; X-ray crystallography;

Metal carboxylate complexes of L-3-phenyl-2-(3-phenyl-ureido)-propionic acid by Anirban Karmakar; Jubaraj B. Baruah (140-144).
The L-3-phenyl-2-(3-phenyl-ureido)-propionic acid (LH) has syn–syn conformation around urea group and has R 1 2 (6) hydrogen bonding pattern. The urea part of the ligand in its sodium complex [NaL(H2O)3]2 adopts an anti–syn conformation. The corresponding carboxylato bridged polymeric cadmium and manganese complexes of L, [ML2(H2O)2] n where M = Cd and Mn have syn–syn conformation on urea part.The L-3-phenyl-2-(3-phenyl-ureido)-propionic acid (LH) and cadmium, manganese complexes of L, [ML2(H2O)2] n has syn–syn conformation around urea group whereas in a dinuclear sodium complex of L [NaL(H2O)3]2 the urea part adopts an anti–syn conformation.
Keywords: Urea derivatives; Carboxylate complexes; Dinuclear sodium complex; Polynuclear manganese complex; Conformers;

Crystal structure, superoxide dismutase activity and electrochemical property of complex [Cu(dtne)] · (ClO4)2  · CH3CH2OH by Qing-Xiang Li; Xiu-Feng Wang; Li Cai; Qiao Li; Xiang-Gao Meng; Ai-Guo Xuan; Shao-Yun Huang; Jun Ai (145-147).
A new copper complex was prepared and characterized X-ray crystallography. The activity of SOD and electrochemical property of the complex has been researched.A new copper (II) complex [Cu(dtne)] · (ClO4)2  · CH3CH2OH, where dtne is 1,2-bis(1,4,7-triaza-1-cyclononyl)ethane, was prepared and characterized by X-ray crystallography. The result shows that in the complex the copper (II) adopts an octahedral coordination geometry. The cyclic voltammetry of the complex recorded in aqueous solution indicates a reversible one-electron redox reaction. The activity of dismutation of superoxide ( • O 2 - ) of the complex in the riboflavin–methionine–nitro blue tetrazolium assay has been researched.
Keywords: Crystal structure; Copper (II) complex; Superoxide dismutase mimic; Electrochemical property;

NO2⋯π interaction between the O-atoms of NO2 and pyrazine rings as well as CN⋯π interaction between the N-atom of CN and pyrazine ring is observed in the crystal of 1-(4′-nitrobenzyl)pyrazinium bis(maleonitriledithiolato)nickelate(III).A charge-transfer compound, [NO2BzPz][Ni(mnt)2] (NO2BzPz+  = 1-(4′-nitrobenzyl)pyrazinium and mnt2−  = maleonitriledithiolate), has been structurally characterized, which shows rare noncovalently intermolecular interactions between lone-pair electron and electron-deficient pyrazine rings (NO2⋯π and CN⋯π), theoretical analysis reveals that such intermolecular interactions can be attributed to Coulomb interaction. The paramagnetic [Ni(mnt)2] anions in [NO2BzPz][Ni(mnt)2] form a dimerized stack and strong antiferromagnetic coupling interaction is observed in such a spin dimer which lead to weak paramagnetic feature in this compound.
Keywords: Bis(maleonitriledithiolato)nickelate monoanion; Crystal structure; Lone-pair⋯π interaction; Magnetic property; DFT calculation;

The near-infrared optical properties of an Nd (III) complex and its potential application in electroluminescence by Zhefeng Li; Jiangbo Yu; Liang Zhou; Ruiping Deng; Hongjie Zhang (151-153).
NIR electroluminescent property of an Nd3+ complex was studied and the maximum NIR irradiance was obtained as 2.1 mW/m2 at 16.5 V.A trivalent neodymium ion (Nd3+) complex Nd(PM)3(TP)2 was synthesized, and its optical properties was studied by introducing Judd–Ofelt theory to calculate the radiative transition rate and the radiative decay time of the 4F3/2  →  4I J transitions in this Nd(III) complex. The strong emissions of this complex at near-infrared region were owing to the efficient energy transfer from ligands to center metal ion. The potential application of this complex in NIR electroluminescence was studied by fabricating several devices. The maximum NIR irradiance was obtained as 2.1 mW/m2 at 16.5 V.
Keywords: Near-infrared; Nd (III) complex; Electroluminescence;

Ferromagnetic interactions in a bis(μ-end-on azido)cobalt(II) linear trimer by Xun Lin; Jun Tao; Rong-Bin Huang; Lan-Sun Zheng (154-156).
A new linear trinuclear Co(II) compound containing end-on azide bridging ligands was structurally characterized, variable temperature magnetic susceptibility studies indicated ferromagnetic interactions between adjacent Co(II) atoms.A linear trinuclear Co(II) compound, [Co31,1-N3)4(N3)2(H2O)2(bpbp)2] · 2H2O (1, bpbp = 3,3′-bis-Dimethylamino-1,1′-pyridine-2,6-diyl-bispropenone), is reported. The central Co(II) ion is bridged to Co(II) ions on both sides by four end-on azide ( μ 1 , 1 - N 3 - ) ligands resulting in a centrosymmetric trimer with adjacent Co⋯Co distance of 3.233 Å. Each Co(II) ion possesses distorted octahedral geometry, the central one is coordinated by two aqua ligands and four μ 1 , 1 - N 3 - nitrogen atoms and each terminal Co(II) is coordinated by two μ 1 , 1 - N 3 - nitrogen atoms, one terminal N 3 - nitrogen atom and capped by terminal tridentate bpbp ligand. Variable temperature magnetic studies indicate ferromagnetic coupling between adjacent Co(II) ions within the trimer.
Keywords: Trinuclear compound; Azide; Ferromagnetic interaction; Cobalt(II);

A new 2D brickwall architecture was first constructed from a double-T-shaped ligand (H4BPTC) as the spacer and tetra-/pentacoordinate copper ions as nodes, which exhibits framework dynamic upon de-/resolvation.A double-T-shaped ligand (H4BPTC) as the spacer has been first used to direct the assembly of a 2D coordination polymer with brickwall network topology, [Cu2(BPTC)(Im)4(H2O)(DMF)] n (1) (DMF =  N,N-dimethylformamide, H4BPTC = Biphenyl-3,3′,4,4′-tetracarboxylic acid, Im = imidazole), which exhibits an interesting framework dynamic upon de-/resolvation.
Keywords: Coordination polymer; Brickwall; Double-T-shaped ligand; Framework dynamic;

A ferrocene-based multi-signaling sensor molecule functions as a molecular switch by Veeramuthu Stalin Elanchezhian; Muthusamy Kandaswamy (161-165).
A multi-channel signaling cation sensor R had been achieved by covalently connecting ferrocene unit to the nitrogen (C=N) containing binding site. Ferrocene-based sensor R was synthesized and characterized by spectroscopic methods and single crystal XRD. The chromogenic, flourogenic and electrochemical sensor study of R in CH3CN shows selective binding of Cu2+ ion. Inherently molecule R performs as molecular switch beyond the sensing role.A multi-channel signaling cation sensor R had been achieved by covalently connecting ferrocene unit to the nitrogen (C=N) containing binding site. Ferrocene-based sensor R was synthesized and characterized by spectroscopic methods and single crystal XRD. The chromogenic, flourogenic and electrochemical sensor study of R in CH3CN shows selective binding of Cu2+ ion. Inherently molecule R performs as molecular switch beyond the sensing role.
Keywords: Chemosensor; Multi-channel signaling; Molecular switch and cation sensor;

Two corrugated 2D bilayer (63)(658) topological coordination polymers: Synthesis, structure, and water-induced reversible transformation by Yunxia Hu; Wenwei Zhang; Xiaofei Zhang; Zhilin Wang; Yizhi Li; Junfeng Bai (166-168).
Two stable supramolecular microporous polymers with rarely (3,4)-connected (63)(658) topology, [Co(AIP)(BPY)0.5  · H2O] n  · 2nH2O (1) and [Ni(AIP)(BPY)0.5  · H2O] n  · 2nH2O (2), (AIP = 5-aminoisophthalate, BPY = 4,4′-bipyridine), have been synthesized under hydrothermal conditions. Both of them represent interesting water-induced reversible transformation properties confirmed by PXRD studies.Two stable supramolecular microporous polymers with double-layer structures, [Co(AIP)(BPY)0.5  · H2O] n  · 2nH2O (1) and [Ni(AIP)(BPY)0.5  · H2O] n  · 2nH2O (2), were constructed from AIP (5-aminoisophthalate) and BPY (4,4′-bipyridine) under hydrothermal conditions. Both of them exhibit rarely reported (3,4)-connected (63)(658) topology and interesting water-induced reversible transformation properties that are confirmed by PXRD studies.
Keywords: Coordination polymer; Microporous material; Crystal structure; Desorption/adsorption;

Two novel supramolecular isomers based on 2,2′-biimidazole derivative and zinc ions: Syntheses, structures and luminescent properties by Yan-Hong Xu; Ya-Qian Lan; Ya-Hui Zhao; Dong-Ying Du; Guang-Juan Xu; Kui-Zhan Shao; Zhong-Min Su; Yi Liao (169-172).
Two novel supramolecular isomers with their formulas as [Zn(L)] · 2H2O, have been prepared by hydrothermal reaction. Complex 1 shows a 2D grid and complex 2 exhibits an interesting twofold interpenetrated 3D network structure. Moreover, two complexes both exhibit good room-temperature phosphorescence emissions.Two Zn(II)-2,2′-biimidazole derivative supramolecular isomers 1 and 2 formulated as [Zn(L)] · 2H2O (H2L  =  4,4′-(1H,1′H-2,2′-biimidazole-1,1′-diylbis(methylene))dibenzoic acid) have been synthesized, and structurally characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography. Complex 1 exhibits a 2D four-connected network with (43.63) topology when the zinc center and the L2− ligand act as four-connected nodes (or a distorted (4,4) grid if the [Zn2(imidazole)4] units are considered as four-connected nodes). Complex 2 shows a novel four-connected twofold interpenetrated net with (42.62.82) topology when the zinc center and the L2− ligand act as four-connected nodes (or a twofold interpenetrated α-Po topology when [Zn2(imidazole)4] units are identified as six-connected nodes). Moreover, complexes 1 and 2 both exhibit strong luminescent properties at room temperature.
Keywords: Supramolecular isomers; Zn(II); 2,2′-Biimidazole; Topology; Luminescent property;

Interplay between nitronates and nitriles accomplished in a PtIV-mediated reaction by Nadezhda A. Bokach; Sema L. Ioffe; Fedor M. Dolgushin; Mikhail Yu. Antipin; Vladimir A. Tartakovskii; Vadim Yu. Kukushkin (173-176).
Interplay between trans-[PtCl4(EtCN)2] and the cyclic nitronate gives the N-acylated iminocomplex which undergoes hydrolysis in nondried solvents.Reaction between the coordinated propanenitriles in trans-[PtCl4(EtCN)2] and the cyclic nitronate ▪ (1) gives the N-acylated iminocomplex ▪ (2) which is unstable in wet solvents and undergoes hydrolysis to furnish ▪ (3). The formulation of 2 and 3 was supported by satisfactory C, H, and N elemental analyses, agreeable HRESI+-MS, IR, 1H NMR spectroscopies, and single-crystal X-ray diffraction (for trans-3).
Keywords: Nitronates; Nitriles; Platinum(IV) complexes; Ligand reactivity; Metal-mediated reaction;

Formation of three-dimensional supramolecular water architectures containing 1D water chains via dianion templating by Hui-Duo Xian; Hua-Qiong Li; Xia Shi; Jian-Feng Liu; Guo-Liang Zhao (177-180).
A novel three-dimensional supramolecular water architectures: [Ni(C10H16O4)(C10H18O4)0.5(phen)3] · 11H2O (1) [C10H16O4  = sebacic dianion, C10H18O4  = sebacic acid, phen = 1,10-phenanthroline] has been synthesized and characterized by IR, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffractions. 1D water chains behave as pillars to join these water sheets to make an overall three-dimensional supramolecular architecture by hydrogen-bonding interactions.A three-dimensional supramolecular water architectures: [Ni(phen)3](C10H16O4) · (C10H18O4)0.5  · 11H2O (1) [phen = 1,10-Phenanthroline, C10H16O4  = sebacic dianion, C10H18O4  = sebacic acid] has been synthesized and characterized by IR, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffractions. 1D water chains behave as pillars to join these water sheets to make an overall three-dimensional supramolecular architecture by hydrogen-bonding interactions.
Keywords: Sebacic acid; Nickel complex; Water chains; Crystal structure;

The sulfate dianions in compound 1 display three types of coordination fashions and each plays a different role, which is the first example in the family of metal sulfates with 4,4′-bipyridine.Two new noncentro symmetric inorganic–organic composite materials have been obtained by reactions of metal (Ni or Fe) sulfate salts and 4,4′-bpy (bpy = bipyridine). X-ray single-crystal diffraction analyses reveal that in compound 1, sulfate dianions show three kinds of coordination modes and act not only as ligands bound to metal sites but also as charge-compensating and space-filling species. The void of the cavities in 1 is estimated to be about 13.5% by PLATON calculation when the lattice waters are removed. The structure of compound 2 exhibits one-dimensional infinite chains in which the –Fe–bpy– chain subunits are interconnected by hydrogen-bonding interactions and π–π stacking interactions.
Keywords: Noncentro symmetric; 4,4′-Bipyridine; Sulfate; X-ray diffraction analysis; Coordination mode;

Synthesis, characterization and compared reactivity of asymmetrical ansa-metallocenes by Carlos Alonso-Moreno; José Sancho; Fernando Carrillo-Hermosilla; Antonio Otero; Antonio Antiñolo; Isabel López-Solera (184-186).
Synthesis of a new family of asymmetrical Me2Si-bridged ansa-indenyl metallocenes substituted in 3-position by alkyl groups is described. Preliminary results in homogeneous polymerization of ethylene and in heterogeneous copolymerization of ethylene and 1-hexene have been achieved. Rac and meso ansa-zirconocenes [Zr{1-Me2Si(3-R-(η5-C9H5))(3-R′-(η5-C9H5))}Cl2] (R = Et, R′ = H; R = Pr, R′ = H; and R = Et, R′ = Pr) 49 have been prepared by the reaction of ZrCl4 with the corresponding dilithiated derivatives from the ligands {1-Me2Si(3-R-(η5-C9H5))(3-R′-(η5-C9H5))} (R = Et, R′ = H 1; R = Pr, R′ = H 2; and R = Et, R′ = Pr 3) in diethyl ether/toluene at −78 °C. The molecular structure of rac [Zr{1-Me2Si(3-Et-(η5-C9H5))(3-Pr-(η5-C9H5))}Cl2] 8 has been determined by single crystal X-ray diffraction studies, which show a pseudotetrahedral environment formed by the two chlorine ligands and two η5-coordinated indenyl ligands. The activity in homogeneous and heterogeneous polymerization is compared and discussed.
Keywords: Metallocene; Supported catalysts; Copolymerization;

A lead(II) orotate complex [Pb(HOr)(H2O)] n (1), (H3Or = orotic acid) was synthesized under hydrothermal condition. Lead atom in 1 is in a holodirected eight-coordinated polyhedron and the orotate ligand exhibits a new and unique hexametallic coordination mode. The lead complex shows a 6,6-connected (48, 66, 8)(413, 62) topology.A lead(II) orotate complex [Pb(HOr)(H2O)]n (1), (H3Or = orotic acid) was synthesized under hydrothermal condition and characterized by X-ray diffraction, IR, solid-state photoluminescence and thermogravimetric analysis. Lead atom in 1 is in a holodirected eight-coordinated polyhedron and the orotate ligand exhibits a new and unique hexametallic coordination mode. The lead complex shows a 6,6-connected (48, 66, 8)(413, 62) topology. The complex exhibits photoluminescence at 546 nm (λ ex  = 350 nm).
Keywords: Lead(II); Complex; Crystal structure; Topology; Luminescent property;

A two-dimensional lanthanide-suberate has been synthesized via hydrothermal methods. This structure is composed of dimeric secondary building units that are extended into sheets by suberate anions. Direct photoexcitation of the lanthanide center (Eu(III) and Tb(III)) show typical emission characteristics.A two-dimensional lanthanide-suberate has been synthesized via hydrothermal methods. This structure is composed of dimeric secondary building units that are extended into sheets by suberate anions. Direct photoexcitation of the lanthanide center (Eu(III) and Tb(III)) show typical emission characteristics.
Keywords: Lanthanide; Luminescence; Coordination polymer; Hydrothermal synthesis;