Inorganic Chemistry Communications (v.44, #C)

Contents List (iii-xv).

Nano-structures of one-dimensional supramolecular polymer, [Ag(Me-8-HqH)(Me-8-Hq)]n (1) [Me-8-HqH = 2-methyl-8-hydroxyquinoline], have been synthesized by the reaction of Me-8-HqH and AgNO3 by sonochemical process. The single-crystal X-ray data of compound 1 shows that both two AgI ions are chelated by two Me-8-HqH and Me-8-Hq molecules. Coordination number of AgI ions in compound 1 is four and they have AgO2N2 coordination sphere. The AgI complexes in 1 are linked to each other via hydrogen bonding and form a supramolecular chain structure. Thermal decomposition of compound 1 nanostructure in oleic acid results in formation of silver nano-structure. These nano-structures were characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The thermal stability of compound 1 was studied by thermogravimetric (TG) and differential thermal analyses (DTA).Nano-structure of an Ag(I) complex has been synthesized and characterized. The AgI complexes are linked to each other via hydrogen bonding and form a supramolecular chain structure. Thermal decomposition of silver(I) polymer nano-structure in oleic acid results in the formation of silver nano-structure.Display Omitted
Keywords: Supramolecular polymer; Nano-structure; Nanosilver; Sonochemical; Surfactant; Oleic acid;

Two novel Se/O mixed-donor molecular probes based on ferrocene and anthracene units by Jing Shen; Tong Liu; Yu Li; Wei Ji; Su Jing; Dun-Ru Zhu; Guo-Feng Guan (6-9).
Two mixed-donor molecules containing ferrocene and anthracene moiety, 1 and 2, have been designed and synthesized as potential multichannel probes for transition metal cations. They displayed switch-on fluorescence intensity only with Cu2 + among the metal ions examined. Electrochemistry and UV–vis spectra studies showed that Cu2 + induces the oxidation of ferrocene unit and then forms stable Cu+ complex.Two mixed-donor multichannel molecular probes were synthesized. They displayed switch-on fluorescence intensity with Cu2+, due to Cu2+ oxidation of ferrocene unit and the formation of stable Cu+ complex.Display Omitted
Keywords: Ferrocene; Anthracene; Multichannel probe; Cu2 +;

Supported palladium nanoparticles on Mn-carboxylate coordination polymer (Pd/MnBDC) were prepared using solution impregnation method. This new catalyst was characterized by XRD, SEM, TEM, EDX, XPS, FTIR and TGA analysis. The Pd/MnBDC exhibits efficient catalytic activity for the Mizoroki–Heck coupling reaction between iodobenzene and either aromatic or aliphatic terminal alkenes and reuses up to four runs without significant loss of activities.Supported palladium nanoparticles on Mn-carboxylate coordination polymer (Pd/MnBDC) were prepared using solution impregnation method. The Pd/MnBDC with anaverage size of 7 nm exhibit efficient catalytic activity for the Mizoroki–Heck coupling reaction between iodobenzene and either aromatic or aliphatic terminal alkenes. This heterogeneous catalyst was used for 4 cycles efficiently.Display Omitted
Keywords: Palladium nanoparticles; Heterogeneous catalyst; Mizoroki–Heck coupling reaction; Manganese coordination polymer;

The first 3D POMOF based on α-metatungstate and mixed-ligand by Shaobin Li; Huiyuan Ma; Haijun Pang; Li Zhang; Zhuanfang Zhang; Huangding Lin (15-19).
A new three-dimensional (3D) POMOF based on α-metatungstate and mixed-ligand, [Cu4(pzta)2(bipy)4(H2O)6][H2W12O40]·2H2O (1) (pzta = 5-(2-pyrazinyl) tetrazole, bipy = 4,4′-bipyridine), has been synthesized and characterized by routine methods. In 1, there is a 2D inorganic layer constructed by W12 clusters and copper cations, which is reinforced by the incorporation of the dinuclear copper complexes to form a poly-pendant layer. Furthermore, the dicoordinated bipy ligands as pillars link parallel neighboring poly-pendant layers to generate a novel 3D framework with a (65  · 81)2(67  · 87  · 121) topology. To the best of our knowledge, it represents the first 3D POMOF constructed by α-metatungstate and mixed-ligand. In addition, the electrochemical studies show that 1 has a good electrocatalytic activity toward reduction of nitrite.A new POMOF has been synthesized, which represents the first example of 3D POMOF based on α-metatungstate and mixed-ligand.Display Omitted
Keywords: Polyoxometalate; Metatungstate; Mixed-ligand; Electrocatalytic activity;

A series of chiral Mn (III) salen are anchored on ZnPS-PVPA modified by onium salt and characterized. In the asymmetric epoxidation of unfunctionalized olefins with m-CPBA and NaIO4 as oxidants, the supported catalysts demonstrate higher catalytic activities than those of the corresponding homogeneous chiral Mn (III) salen catalyst under the same conditions both for experimental scale and for large-scale reactions. Moreover, the catalysts are stable could be recycled nine times without significant loss of activity, which are provided with the potentiality for application in industry.The catalysts immobilized salen Mn (III) onto ZnPS-PVPA displayed superior catalytic ability both for experimental scale and for large-scale reactions.Display Omitted
Keywords: Zinc poly (styrene-phenylvinylphosphonate)-phosphate; Axial base; Salen Mn (III); Heterogeneous catalysts; Asymmetric epoxidation;

Under solvothermal condition, the reaction of Co(II) or Zn(II) acetate with mixed-ligands 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole (Hppt) and 1,2,4,5-benzenetetracarboxylate (H4btec) affords two isomorphic compounds [M(btec)0.5(Hppt)]n (M = Co(II) (1), Zn(II) (2)), which display the same dinodal (4,4)-connected 2D net. In addition to single-crystal X-ray crystallography, the complexes are also characterized by IR spectroscopy, PXRD, thermogravimetry, and elemental analysis. Magnetic susceptibility measurements indicate that domain antiferromagnetic interaction exists between Co(II) ions, and the paramagnetic behavior in 1 can be observed. The fluorescent property of 2 has been investigated in the solid state at room temperature.Under solvothermal condition, the reaction of Co(II) or Zn(II) acetate with mixed-ligands 3-(pyridin-4-yl)-5-(pyrazin-2-yl)-1H-1,2,4-triazole (Hppt) and 1,2,4,5-benzenetetracarboxylate (H4btec) affords two isomorphic 2D net compounds.Display Omitted
Keywords: Iomorphic compounds; Benzenetetracarboxylate; Magnetic property; Fluorescent;

A new acrylamide MOF with sra net showing an uncommon eight-fold interpenetration by Shu-yun Huang; Jian-qiang Li; Xiao-liu Wu; Xiao-min Zhang; Ming-biao Luo; Feng Luo (29-31).
A new acrylamide coordination polymer, namely, Zn(L)(tp)·2H2O(1) (L = N1,N4-di(pyridin-4-yl)naphthalene-1,4-dicarboxamide, H2tp = terephthalic acid), was obtained by hydrothermal self-assembly. Topological analysis reveals a common sra-type matrix but shows an uncommon interpenetrating mode of eight-fold interpenetration in the (4 + 4) fashion. Furthermore, fluorescence and thermogravimetry analyses have been investigated in detail.We present here a common sra net but shows an uncommon interpenetrating mode of eight-fold interpenetration in the (4 + 4) fashion, featuring (42·63·8) topology symbol.Display Omitted
Keywords: Acrylamide coordination polymer; Hydrothermal synthesis; Four-connected; Eight-fold interpenetration; sra net;

SynopsisPu atom is at the inversion center of the PuO2L2(ClO4)2 complex where L stands for N,N,N’,N’-tetrtametryl-3-oxa-glutaramide (TMOGA). Due to the forbiddance of the f-f transitions, PuO2L2(ClO4)2 in solution is “silent” in near IR optical absorption and PuO2L2(ClO4)2 in solid does not have significant diffuse reflectance bands.The variation of the absorption spectra of Pu(VI) in the presence of a tridentate organic ligand, N,N,N′,N′-tetramethyl-3-oxa-glutaramide (TMOGA denoted as L), was interpreted with the assumption that the 1:2 complex, PuO2L2(ClO4)2, is “silent” in optical absorption of the near IR region because the f–f transitions of Pu(VI) are forbidden due to the high symmetry of the complex. To test the assumption and demonstrate the validity of the Laporte's rule that governs the probability of f–f transitions, crystals of the PuO2L2(ClO4)2 complex were synthesized from the aqueous solution and characterized with single-crystal X-ray diffraction and diffuse reflectance spectra. The structural data, showing that the square-based prism salt crystallized in a highly symmetrical tetragonal space group, I4/mcm, and the plutonium atom is on a center of inversion at the intersection of three perpendicular mirror planes, support the above assumption. The diffuse reflectance spectra of the solid PuO2L2(ClO4)2 also showed no significant bands in the near IR region, consistent with the “silent” feature in the absorption spectra of this complex in solution.Pu atom is at the inversion center of the centrosymmetric complex, PuO2L2(ClO4)2 where L stands for the trident ligand, N,N,N′,N′-tetramethyl-3-oxa-glutaramide (TMOGA). Due to the forbiddance of the f–f transitions, PuO2L2(ClO4)2 in solution is “silent” in optical absorption of the near IR region, and PuO2L2(ClO4)2 in solid does not have significant diffuse reflectance bands in the near IR region.Display Omitted
Keywords: Pu(VI); Complexation; Optical absorption; Symmetry;

The first mononuclear copper(II) complexes [N(Dipp)C(NMe2)NC(NMe2)N(SiMe3)]CuCl (Dipp = 2,6-iPr2-C6H3) (2) and [N(Ph)C(NMe2)NC(NMe2)N(SiMe3)]2Cu (3) with 1,3,5-triazapentadienyl ligands have been synthesized and structurally characterized by X-ray crystallography and spectroscopic techniques. The X- ray structures of 2 and 3 show that they crystallize in the triclinic system. Trigonal planar structure is observed for the Cu(II) center in 2 and a square-planar environment in 3. The magnetic properties of 2 and 3 have been investigated.Novel copper(II) salts of [N(Dipp)C(NMe2)NC(NMe2)N(SiMe3)]CuCl (Dipp = 2,6-iPr2-C6H3) and [N(Ph)C(NMe2)NC(NMe2)N(SiMe3)]2Cu are reported. Their structural features are discussed and their magnetic properties have been studied.Display Omitted
Keywords: Triazapentadienyl; Cu(II) complex; Crystal structure; Magnetic property;

The reaction of Zn(NO3)2, 1,4-bis(1,2,4-triazol-4-yl)benzene (btx), 1,4-benzenedicarboxylicate (1,4-bdc) or fumarate (fum) gives two unusual coordination polymers {[Zn(btx)(1,4-bdc)] 3H2O}n (1) and [Zn(btx)0.5(fum)(H2O)]n (2). 1 shows a 5-fold interpenetrated three-dimensional diamondoid network. 2 displays a 2D → 3D inclined polycatenation motif consisting of two sets of equivalent 2D (6,3) layers. The luminescence and thermal stability were investigated.Two zinc(II) coordination polymers showing a 5-fold interpenetrated three-dimensional diamondoid network and a 2D → 3D inclined polycatenation motif consisting of two sets of equivalent 2D (6,3) layers were synthesized and characterized.Display Omitted
Keywords: Diamondoid network; Polycatenate; 5-Fold interpenetrated; Zinc coordination polymer; Luminescence;

Two Bi-based phosphate photocatalytic materials Na3Bi2(PO4)3 and Na3Bi(PO4)2 have been successfully synthesized by a solid-state reaction. Compared to BiPO4 with band gap 3.77 eV, the introduction of Na3PO4 resulted in smaller band gaps of 3.6 and 3.01 eV for Na3Bi2(PO4)3 and Na3Bi(PO4)2, respectively. The photocatalytic activities of the samples were determined by photooxidative decomposition of methylene blue (MB) in aqueous solution. The results revealed that both Na3Bi(PO4)2 and Na3Bi2(PO4)3 can be used as effective photocatalysts under UV irradiation, and the former exhibits a higher photocatalytic activity compared to BiPO4, which may be attributed to more light absorption in the UV range. It is a novel way to regulate the band-gaps of semiconductors and explore new photocatalytic materials.Two novel Bi-based phosphate photocatalysts Na3Bi2(PO4)3 and Na3Bi(PO4)2 were successfully developed. The design for Bi-based phosphates with narrow band gaps has been realized.Display Omitted
Keywords: Semiconductor; Na3Bi2(PO4)3; Na3Bi(PO4)2; Band gap; Microstructure;

Unpredictable reaction of phenyltrichlorosilane with tert-butyllithium by Stefan Scholz; Inge Sänger; Frauke Schödel; Michael Bolte; Hans-Wolfram Lerner (50-52).
The reaction of PhSiCl3 with one equivalent of Li[tBu] at r. t. yielded tBuPhSiCl2 whereas tBu2PhSiCl was only a minor product of the reaction of two molar equivalents Li[tBu] with PhSiCl3 at 60 °C. By contrast, at r. t. tBuPhSiCl2 was solely formed by this reaction. Treatment of PhSiCl3 with three or more equivalents of Li[tBu] at 98 °C yielded a mixture of tBu2PhSiH and tBu2(tBuC6H4CMe2CH2)SiH (3). Both silanes could easily be separated from each other: tBu2PhSiH was distilled from the reaction mixture and the silane 3 could be crystallized from the dissolved distillation residue. X-ray quality crystals of 3 were grown from a benzene solution at ambient temperature (monoclinic, P21/c).Display Omitted
Keywords: tert-Butyllithium; Silanes; Silenes; X-ray structure analysis;

Construction of two Zn(II) complexes based on the oxime-containing Schiff base ligand with NO and N2O donor sets by Xu-Jia Hong; Qing-Guang Zhan; Zhuang-Peng Huang; Yuan-Qi Du; Lei-Ming Wei; Teng Li; Zhi-Peng Zheng; Yue-Peng Cai (53-57).
Two zinc(II) complexes with NO- and N2O-set oxime-containing Schiff base ligand of 2-hydroxyimino-N′-[1-(2-pyridyl)ethylidene]propanohydrazone (Hpop), namely [Zn3(pop)2-(CH3OH)2Cl4] (1) and [Zn(pop)Cl]4·(H2O)2 (2), have been successfully synthesized from the reaction of Hpop with ZnCl2 in CH3OH under different temperatures and fully characterized by X-ray single-crystal diffraction, EA and IR as well as TG. At the low temperature, the linear M3L2-type trinuclear Zn(II) compound 1 was obtained, however, the grid-like Zn4L4-type tetranuclear Zn(II) compound 2 was given at the high temperature from the same reactants. Interestingly, compound 1 may be irreversibly transformed into 2 via ring-closed coordination reaction under the high temperature, accompanied by the corresponding changes in fluorescent property.Two temperature-dependent Zn(II) complexes with NO- and N2O-set oxime-containing Schiff base ligand of Hpop have been successfully synthesized via different strategies and fully characterized, in which two complexes 1 and 2 have different fluorescent characteristics.Display Omitted
Keywords: Polynuclear zinc(II) compounds; Syntheses and conversion; 2-Hydroxyimino-N′- [1-(2-pyridyl)ethylidene]propanohydrazone; Ring-closed coordination reaction; Fluorescence;

Syntheses, structures and luminescent properties of the metal complexes based on Zn(II) or Cd(II) with 5-nitro-8-hydroxyquinoline by Hong-Ling Gao; Shu-Xin Jiang; Yao-Min Hu; Fang-Fang Li; Qin-Qin Zhang; Xue-Ying Shi; Jian-Zhong Cui (58-62).
Five new complexes of Cd(II) and Zn(II), [M(C9H5N2O3)2(CH3OH)2] (1, 2) and [M(C9H5N2O3)2(C2H8N2)] (3, 4) (M = Zn(II) and Cd(II)) and [Zn(C9H5N2O3)2(C10H8N2)] (5), have been prepared by the slowly release methods of 5-nitro-8-hydroxyquinoline from 5-nitro-quinoline-8-yl acetate and characterized by elemental analysis, IR, thermal gravimetric analysis, fluorescence measurement and single crystal X-ray diffraction analysis. All the complexes are mononuclear and show excellent luminescence properties in the solid state at room temperature.Display Omitted
Keywords: 5-Nitro-quinoline-8-yl acetate; Metal complexes; Zinc; Cadmium; Luminescent properties;

Room temperature crystallization of trichlorodioxouranate [UO2Cl3(L)] species in molecular assemblies involving aliphatic dicarboxylate linkers by Ionut Mihalcea; Clément Falaise; Christophe Volkringer; Natacha Henry; Thierry Loiseau (63-66).
Three uranyl carboxylates (UO2)2Cl6(succ)·4dmaH (1), (UO2)2Cl6(adip)·4dmaH (2) and (UO2)2Cl6(1,4-chdc)·4dmaH (3) have been synthesized from slow evaporation in ambient atmosphere of solutions of aliphatic carboxylic acids and UCl4 in N,N-dimethyformamide (DMF) after a solvothermal treatment (succ = succinate, adip = adipate, 1,4-chdc = 1,4-cyclohexanedicarboxylate, dmaH = monoprotonated dimethylamine). These three compounds possess a similar crystal structure based on the molecular assembly of discrete dinuclear motifs (UO2)2Cl6(L) separated by dimethylammonium cations (coming from the in situ decomposition of DMF). Hexavalent uranium cation is found in seven-fold coordination (pentagonal bipyramid) with the typical double uranyl bond. Three chloride anions and two carboxyl oxygen atoms are located in the equatorial pentagonal plane, resulting in a trichlorodioxouranate ‘UO2Cl3(OC)2’ tecton. The uranyl centers are linked to each other through the ditopic ligand via the two carboxylate arms. The three compounds have been characterized by infrared and luminescence spectroscopies.Three uranyl carboxylates, (UO2)2Cl6(L)·4dmaH, have been isolated from slow evaporation under air atmosphere of solutions after solvothermal reactions of UCl4 and α,ω-dicarboxylic acid (LH2 = succinic, adipic and 1,4-cyclohexanedicarboxylic acids) in N,N-dimethlyformamide. Their crystal structure revealed molecular assemblies of discrete dinculear units of [UO2Cl3(OC)2] pentagonal bipyramids (hexavalent state for uranium) linked through the ditopic dicarboxylate ligand.Display Omitted
Keywords: Uranyl trichloride; Succinate; Adipate; 1,4-Cyclohexyldicarboxylate; Molecular assembly; Single-crystal X-Ray diffraction;

Palladium(II) thiosemicarbazone complex: Synthesis, structure and application to carbon–oxygen cross-coupling reaction by Pandimuni Kalpaga Suganthy; Rupesh Narayana Prabhu; Venugopal Shanmugham Sridevi (67-69).
A simple route for the synthesis of square-planar palladium(II) 3-methyl-thiophene-2-aldehyde thiosemicarbazone complex is described. The composition of the complex has been established by elemental analysis and spectral methods. The molecular structure was confirmed by single crystal X-ray diffraction study. Further, the complex was used as a potential catalyst for the carbon–oxygen cross-coupling reaction of activating, non-activating and deactivating aryl iodides or aryl bromides with p-cresol.A simple route for the synthesis of square-planar palladium(II) thiosemicarbazone complex is described. The molecular structure was confirmed by single crystal X-ray diffraction studies. Further, the complex was used as a potential catalyst for the carbon–oxygen cross-coupling reaction of activating, non-activating and deactivating aryl iodides or aryl bromides with p-cresol.Display Omitted
Keywords: Thiosemicarbazone ligand; Palladium(II) complex; Crystal structure; Carbon–oxygen cross-coupling;

The synthesis, characterization and the photoinduced electron transfer reactions of the tetranuclear complex cis,fac-[(phen)2Ru(4,4′-bpy)2Mn(CO)3(ImH)]2 +6 (III) and the mononuclear moieties cis-[Ru(phen)2(4,4′-bpy)2]2+ (II) and fac-[Mn(CO)3(4,4′-bpy)2(ImH)]+ (I) in the presence of MV2+ are reported. The intramolecular energy/electron transfer process that occurs between the Ru(II) and the Mn(I) upon MLCT (Ru → phen) light excitation is evaluated by time-resolved absorption experiments. Complex II was not able to reduce MV2+, even in the ns scale. Otherwise, complex III showed an ability to generate MV+ when exposed to flash photolysis irradiation.This work demonstrates the photochemical and photophysical properties of a new tetranuclear complex containing Ru(II) and Mn(I) unities with 4,4′-bpy as bridge ligand.Display Omitted
Keywords: Ruthenium; Manganese; Electron transfer; Energy transfer;

One step molten salt synthesis of YVO4 nanoparticles and their photocatalytic properties under UV–Visible light by Xiaoxin An; You Wang; Jinxia Deng; Jun Chen; Ranbo Yu; Xianran Xing (79-82).
Well-crystalline YVO4 nanoparticles were successfully synthesized by a simple and convenient one-step molten salt synthesis (MSS) method in a wide temperature range of 350–600 °C for only 5 h. The UV–Visible absorption spectra measured by a spectrophotometer suggest that visible light absorption exists in the absorption spectra of all the samples prepared under different temperatures and the smaller the particle size, the stronger the absorption, the smaller the onset of UV absorption and the larger the blue shift. The photodegradation of RB indicates that both particle size and crystallinity have effects on the photocatalytic properties of YVO4 nanoparticles. YVO4 nanoparticles were further demonstrated to have excellent photocatalytic stability.(a) The absorption spectra changes of RB solutions as a function of irradiation time for the sample synthesized at 400 °C for 5 h; (b) Photocatalytic activity for degradation of RB with no catalyst and using the YVO4 nanoparticles synthesized under different calcining temperatures by MSS method.Display Omitted
Keywords: MSS method; Calcining temperature; UV–Visible absorption spectra; Photodegradation; Photocatalytic properties;

Osmocene is intrinsically photoactive. It photolyzes in n-hexane by a reductive elimination leading to the generation of metallic osmium. Moreover, both cyclopentadienyl anions as ligands in osmocene are oxidatively eliminated. Surprisingly, they are liberated as benzene and cyclobutadiene which is trapped by diphenyl acetylene. As a result of this trapping o-terphenyl is formed. It is suggested that in the LF excited state both cyclopentadienyl ligands undergo a bending in agreement with the previous conclusions. The close approach of both ligands facilitates a CH group transfer between them. The subsequent decay generates elemental osmium, benzene and cyclobutadiene as photolysis products.Display Omitted
Keywords: Photochemistry; Photoluminescence; Reductive elimination; Osmocene; Osmium complexes; Cyclopentadienyl complexes;

Four new aluminum chloride complexes {(L1)AlCl}2 (5), {(L2)AlCl}2 (6), (L3)AlCl(THF) (7) and (L4)AlCl(THF) (8) have been prepared by alkane elimination in good yields from the reaction of AlEt2Cl and chiral biaryl Schiff-base NO2 ligands, L1H2L4H2, which are derived from (S)-2-amino-2′-hydroxy-1,1′-binaphthyl or (S)-2-amino-2′-hydroxy-6,6′-dimethyl-1,1′-biphenyl, respectively. Treatment of ligand L1H2 or L2H2 with 1 equiv of AlEt2Cl in benzene gives the binuclear complexes {(L1)AlCl}2 (5) and {(L2)AlCl}2 (6), respectively, in good yields. Reactions of L3H2 or L4H2 with 1 equiv of AlEt2Cl in THF gives the mononuclear complexes (L3)AlCl(THF) (7) and (L4)AlCl(THF) (8), respectively, in good yields. Complexes 58 have been characterized by various spectroscopic techniques, elemental analyses, and X-ray diffraction analyses. The complexes 58 are active catalysts for the polymerization of rac-lactide in the presence of propylene oxide (PO), leading to the heterotactic-rich polylactides.A new series of aluminum complexes have been prepared from chiral biaryl Schiff-base NO2 ligands. The aluminum complexes are active catalysts for the polymerization of rac-lactide, leading to the heterotactic-rich polylactides.Display Omitted
Keywords: Chiral aluminum complex; O2N ligand; Lactide; Polymerization;

Assembly of two-fold interpenetrated silver supramolecular coordination polymer using Keggin phosphotungstate template by He Zhang; Kai Yu; Song Gao; Chunmei Wang; Chunxiao Wang; Haiyan Wang; Baibin Zhou (91-95).
An unusual supramolecular coordination polymer [{Ag(bpy)}2(Hbpy)][PW12O40] (1) has been synthesized under hydrothermal conditions and structurally characterized by elemental analysis, IR, TG, PXRD, XPS, UV–vis, and single-crystal X-ray diffraction. In compound 1, Keggin-type [PW12O40]3 − clusters as templates induce the supramolecular [{Ag(bpy)}2(Hbpy)]3 + layer to 3D hexagonal metal–organic framework (MOF), which represents two-fold interpenetrating MOF with 1-D helical channels constructed from alternate left- and right-handed chains. In addition, compound 1 exhibits good electrocatalytic activity on the reduction of nitrite and fluorescent properties in the solid state at room temperature.Keggin-type [PW12O40]3 − clusters as templates lead to an unusual hybrid material, which presents the first two-fold interpenetrating POMMOF with 1-D helical channels constructed from alternate left- and right-handed chains. The compound displays good electrocatalytic activity on the reduction of nitrite and fluorescent properties in solid state at room temperature.Display Omitted
Keywords: Organic–inorganic hybrid; Supramolecular materials; Electrochemistry and electrocatalytic activity; Fluorescent property;

A new heteroleptic haloplumbate-based inorganic–organic hybrid compound, with a formula [4′-chloro-1-aminopyridinium][Pb3Br5I2], has been synthesized and characterized. This hybrid compound crystallizes in orthorhombic space group Pcca, their inorganic and organic components form respectively layered arrangements. The inorganic anion lamellas (A) and the organic cation layers (C) alternate in the …ACAC… manner along b-axis direction, and the inorganic layer is constructed by the PbBr2I4 and PbBr4I2 octahedra as well as the very rare PbBr8 square antiprisms via sharing the Br–Br or I–I edges and Br–Br–Br triangular faces in the hybrid crystal. To the best of our knowledge, this is the first example that an inorganic layer contains bromide/iodide heteroleptic haloplumbate in a lamellate inorganic–organic hybrid compound. The dielectric property for the hybrid compound was further investigated in the temperature range of 20–150 °C and in the frequency region of 1–107  Hz, indicating the existence of the thermally assisted dynamical dipole motion under ac electric field, which probably originates from the ion hopping. This study will shed a light on the design and preparation of new heteroleptic haloplumbate-based hybrid materials.A new haloplumbate-based inorganic–organic hybrid compound shows layered structure, which inorganic layer is constructed by heteroleptic PbBr2I4 and PbBr4I2 octahedra and very rare PbBr8 square antiprisms, and dynamical dipole motion under ac electrical field.Display Omitted
Keywords: Haloplumbate; Heteroleptic; Lamellate; Hybrid; Dielectric property;

A novel indium complex {[InL(NO3)(OH)] · NO3  · CH3OH}2 (1) is isolated from the refluxing reaction of a tetradentate Schiff base ligand, N,N′-bis(2-pyridinylmethylene)cyclohexane-1,2-diamine (L), and In(III) nitrate hydrate. The room temperature (298 K) and cryogenic temperature (77 K) emission spectra of 1 are recorded in solid state and different solvents (CH3OH, CHCl3, CH3CN and DMSO). Complex 1 exhibits a pronounced bathochromic shift in emission spectra as solvent polarity increases (polarity order: DMSO > CH3CN > CHCl3), indicating a change in dipole moment of 1 upon excitation. Further bathochromic shift exists in CH3OH (467 nm) solution. An extended work is developed to discuss on maximum emission and lunminescent lifetime of 1 dispersed in the deuterated reagents (CD3OD, CDCl3, CD3CN and DMSO-d6 ). The results exhibit that the similar emission also exists in deuterated reagents and the longer lifetime is observed due to the scarcity of O―H, N―H, and C―H oscillators. The quantum yield of 1 decreases with increasing polarity of solvent within the region of 7.8–15.4%. Commission Internationale de L'Eclairage (CIE) 1931 demonstrates that the color gamut of 1 is blue.One novel indium complex {[InL(NO3)(OH)] · CH3OH · NO3}2 is obtained. The emission is sensitive to the polarity of the solvent as well as specific solute–solvent interaction such as hydrogen bonding. In addition, the utilization of deuterated solvents can favor to prolong lifetime.Display Omitted
Keywords: Schiff base; Indium complex; Luminescence; Lifetime; Effect on solvent and temperature;

Coordination site induced controllable assembly of metal–organic units in polyoxometalate-based hybrids by Huan Dong; Yanan Yang; Fangfang Zhao; Wenbin Ji; Beibei Liu; Hailiang Hu; Yang Wang; Hui Huang; Yang Liu; Zhenhui Kang (107-110).
Two hybrid materials based on Keggin-type polyoxometalate, [Ag4(mtrz)4(H2O)2(SiW12O40)] (1), [Ag4(mtez)5(SiW12O40)]·H2O (2), (mtrz = 1-methyl-1,2,4-triazole, mtez = 1-methyl-1,2,3,4-tetrazole), have been hydrothermally synthesized and structurally characterized. Through the use of the azole ligands mtrz and mtez, compounds 1 and 2 with totally different metal–organic units are obtained. In 1, the mtrz ligands with N atoms in meta-positions induced the formation of chain-like metal–organic units, while in 2, the mtez ligands with adjacent N atoms induced the assembly of tetranuclear units. The SiW12 anions act as bridging linkers to evolve the structural dimensionality of the two title compounds into 2D network and 3D framework, respectively.Coordination site induced different unique metal–organic units.Display Omitted
Keywords: Coordination site; Polyoxometalate; Metal–organic unit;

Flexible metal supramolecular framework of 2D cobalt(II) coordination polymer with water-induced reversible crystal-to-amorphous transformation by Jureepan Piromchom; Nanthawat Wannarit; Jaursup Boonmak; Kittipong Chainok; Chaveng Pakawatchai; Sujittra Youngme (111-113).
A new flexible 3D supramolecular framework, [Co(4,4′-bipy)(pro)2(H2O)] (1) (4,4′-bipy = 4,4′-bipyridine and pro = propionate) has been prepared and structurally characterized. This compound crystallizes in monoclinic, space group P21/c. Each Co(II) cation shows an octahedral geometry. The Co(II) ions are assembled by the bridging propionate and 4,4′-bipyridine ligands in c and a axes, generating an infinite 2D layer. These 2D layer networks are further linked to one another by hydrogen bonding interactions, leading to a 3D supramolecular framework. Interestingly, compound 1 exhibits water-induced reversible crystal-to-amorphous transformation with chromotropism confirmed by spectroscopic techniques, elemental analysis, TGA, and XRPD. Thus, dehydrated amorphous form, Co(4,4′-bipy)(pro)2 (1A), may be utilized as an indicator for humidity.A new flexible 3D supramolecular framework, [Co(4,4′-bipy)(pro)2(H2O)] (1); 4,4′-bipy = 4,4′-bipyridine and pro = propionate has been synthesized and fully characterized. This compound exhibits a water-induced reversible crystal-to-amorphous transformation with chromotropism.Display Omitted
Keywords: Cobalt(II); 4,4′-Bipyridine; Propionate; 2D frameworks; Chromotropism; Structural transformation;

Exploring the coordination chemistry of O,N,O′-ligands modified by 2-thienyl-substituents to nickel by Chika I. Someya; Shigeyoshi Inoue; Elisabeth Irran; Stephan Enthaler (114-118).
The coordination chemistry of 5-hydroxypyrazoline ligand class 1 modified by 2-thienyl substituents with Ni(OAc)2 and DMAP as co-ligand to form the nickel complexes 4 [Ni(1-2H)(dmap)x] was investigated. The complexes were characterized and investigated by various techniques, pointing out different complex geometries, octahedral vs. square planar, depending on the connectivity of the 2-thienyl substituent. In more detail, X-ray crystallography revealed an O,N,O′-coordination in which the ligand is planar and the other coordination sites on the nickel center are occupied by one or three DMAP co-ligands, respectively. Moreover, the complexes have been applied as precatalyst in nickel-catalyzed hydrodecyanation reactions.The chemistry of the pyrazol-5-ol ligands 1 containing 2-thienyl groups was studied. 1 forms with Ni(OAc)2 and DMAP the complexes 4 [Ni(1-2H)(DMAP)x]. The position of the 2-thienyl group influences the geometry of the complexes. The complexes we applied in the nickel-catalyzed hydrodehalogenation.Display Omitted
Keywords: Nickel complexes; Tridentate ligands; Nitrogen ligands; Catalysis; Hydrodecyanation;

Self-assembly of an organo-palladium molecular basket that encapsulates cobalticarborane anion in water by Yu-Jiu Mu; Li-Na Yu; Xuan-Feng Jiang; Shu-Yan Yu; Kentaro Yamaguchi (119-123).
Two [M3L3]6 +-type organo-palladium(II) macrocyclic host molecules, {[(phen)Pd]3(4,7-phen)3}(NO3)6, 1·6NO3 ; {[(dtod-phen)Pd]3(4,7-phen)3}(NO3)6, 2·6NO3 , (where M = (4,7-phen)Pd, (dtod-phen)Pd; 4,7-phen = 4,7-phenanthroline (L), phen = 1,10-phenanthroline, dtod-phen = 5,6-di(1′,4′,7′,10′-tetraoxododecanoxy)-1,10-phenanthroline), have been synthesized by metal-directed self-assembly in aqueous solution. These basket-shaped hosts bearing syn, syn, syn orientations and their anion complexes, have been fully characterized by 1H NMR, cold-spray ionization mass spectrometry (CSI-MS) and in the case of basket-shaped host 1*PF6 by X-ray single-crystal diffraction analysis. On the basis of anion binding structure within the cavity of 1, the molecule basket 2 possessing a hydrophobic inner cavity expanded with hydrophilic polyethyleneglycol chains was successfully designed for encapsulating one giant anion [(C2B9H11)2Co] in water and the host–guest interaction was studied by 1H NMR titration and CSI-MS.The molecular basket with a hydrophobic inner cavity and hydrophilic polyethyleneglycol chains can encapsulate one big anion [(C2B9H11)2Co] in water (see picture).Display Omitted
Keywords: Self-assembly; Metallomacrocycles; Anion binding; Palladium;

A new MOF coordination polymer, [(H2O)Cu(BNA)4)Cu(H2O)(BPY)]∙ 5H2O (BNA = 5-bromonicotinato C6H3NO2Br; DPY = 4,4′-dipyridyl C10H8N2), with two distinct metal centers with multifunctional ligands decorating the walls of the framework has been synthesized. The structure is crystallized with the lowest symmetry P1, which displayed an acentric network with inclusion water molecules in the cavities.An acentric coordination polymer with two distinct metal centers with multifunctional ligands decorating the walls of the framework has been synthesized. The structure is crystallized with the lowest symmetry P1 with inclusion water molecules. The MOFs with walls decorated with free sites for possible chemical bindings have attracted more interests.Display Omitted
Keywords: MOF; Two-dimensional; Coordination polymers; Cavity;

Silver(I)-N-heterocyclic carbene complexes of nitrile-functionalized imidazol-2-ylidene ligands as anticancer agents by Rosenani A. Haque; Srinivasa Budagumpi; H. Zetty Zulikha; Noorhafizah Hasanudin; Mohamed B. Khadeer Ahamed; Amin M.S. Abdul Majid (128-133).
Reactions of symmetrically and non-symmetrically substituted nitrile-functionalized imidazolium salts (13) with silver(I) oxide in methanol at room temperature afforded complexes (46) of the type [NHC-Ag-NHC]PF6, (NHC: imidazol-2-ylidene). All reported compounds have been characterized by spectral (1H, 13C NMR and FTIR) and elemental analysis. The structure of bis-imidazolium salt 3 and silver complex 4 was unambiguously elucidated by the single-crystal X-ray diffraction method. The effect of substitutions on the anticancer activity of compounds 1–6 has been investigated by in vitro cytotoxicity studies against human colorectal (HCT 116) cancer cell line, using the MTT assay method. All three silver complexes (46) displayed promising anticancer activity with IC50 values of 6.0 ± 0.2, 14.0 ± 0.6 and 4.0 ± 0.2 μM, while imidazolium salts, 13, showed least (> 200 μM) to moderate (20.3 ± 0.2 and 95.0 ± 2 μM) anticancer potential, respectively. Bis-imidazolium salt 3 and binuclear complex 6 displayed good activity against human breast (MCF-7) cancer line with IC50 values of 82.4 ± 2.5 and 0.9 ± 0.4 μM, respectively.Three N,N′-disubstituted substituted nitrile-functionalized imidazolium salts and corresponding silver(I)–NHC complexes are prepared. All compounds were tested for anticancer activity showing that all three silver complexes are promising anticancer agents.Display Omitted
Keywords: Anticancer potential; Imidazolium salts; MTT assay; N-heterocyclic carbene; Silver(I)–complex; X-ray diffraction;

Metal-catalyzed cross-coupling reactions of iron(II) cage complexes: New furyl-containing macrobicyclic scaffold, a reactive halogenoclathrochelate precursor and its ribbed-functionalized derivatives by Oleg A. Varzatskii; Irina N. Denisenko; Alexander S. Belov; Anna V. Vologzhanina; Yurii N. Bubnov; Sergey V. Volkov; Yan Z. Voloshin (134-138).
Condensation of α-furyldioxime with the macrocyclic iron(II) bis-α-benzyldioximate gave the 2-furyl-containing iron(II) clathrochelate with non-equivalent aromatic chelate fragments. The selective bromination of its furyl ribbed substituents with N-bromosuccinimide afforded the dibromoclathrochelate precursor, Suzuki–Miyaura and Sonogashira reactions of which with 4-carboxyphenylboronic acid and trimethylsilylacetylene in the presence of a generated in situ palladium-containing catalyst gave the target ribbed-functionalized cage complexes with inherent aromatic substituents; aromatic nucleophilic substitution of this precursor with a derivative of piperazine led to the corresponding monofunctionalized iron(II) monobromoclathrochelate. The diamagnetic low-spin iron(II) complexes obtained were characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV–vis, 1H, 11B, 13C and 19F{1H} NMR spectroscopies, and by X-ray diffraction. The FeN6 -coordination polyhedra of X-rayed molecules of clathrochelate scaffold, dibromomacrobicyclic precursor and monofunctionalized iron(II) monobromoclathrochelate possess a similar distorted trigonal prismatic–trigonal antiprismatic geometry with the distortion angles φ of approximately 26°; their heights h and the bite angles α are approximately 2.31 Å and 39.0°. So, metal-catalyzed cross-coupling reactions of a dibromine derivative of the new furyl-containing tris-dioximate iron(II) clathrochelate have been successfully used, for the first time, for the synthesis of ribbed-functionalized cage complexes with inherent functionalized aromatic substituent(s). This expands our ability to create clathrochelate complexes of different structures, symmetries and functionalities that meet criteria for practical use as transcription inhibitors, DNA intercalators as well as versatile entities for molecular (photo)electronic devices; the monofunctionalized iron(II) cage complex seems to be a suitable bromoclathrochelate precursor for further functionalization via metal-catalyzed reactions.Suzuki–Miyaura and Sonogashira cross-coupling reactions of 5-bromo-2-furyl groups of a reactive furyl-containing halogenoclathrochelate precursor have been used, for the first time, for the synthesis of ribbed-functionalized iron(II) clathrochelates with inherent functionalized aromatic substituent(s).Display Omitted
Keywords: Macrocyclic compounds; Clathrochelates; Ligand reactivity; Sonogashira reaction; Suzuki–Miyaura reaction;

Highly stable methylaluminum dimer complex with chiral tridentate ligand by Min Jeong Go; So Han Kim; Yi Young Kang; Hyoung-Ryun Park; Youngjo Kim; Junseong Lee (139-142).
The dimeric aluminum complex containing fully deprotonated 4-{[(1S,2R)-2-hydroxyindan-1-yl]amino}-pent-3-en-2-one was synthesized and characterized. X-ray analysis revealed that the two five-coordinate aluminum centers possess ideal tetragonal pyramid geometry and two methyl groups are located in cis position. It is found to be stable in the presence of isopropanol at room temperature. The compound was used as a catalyst for the ring opening polymerization of lactide accompanying lactide epimerization.A dimeric aluminum complex was simply prepared and confirmed by various spectroscopic methods. X-ray crystallography reveals that the complex forms a dimeric species with two bridged oxygen atoms in which two methyl groups are located in cis position. It was proven as an effective catalyst for the controlled ring opening polymerization of lactide, and lactide epimerization was observed.Display Omitted
Keywords: Chiral ligand; Schiff base ligand; Dimeric aluminum complex; Ring opening polymerization; Polylactide; Epimerization;

A 3D cadmium(II) coordination polymer constructed from new β-diketone-functionalized pyridinecarboxylate and 4,4′-bipyridine ligands by Qing Chen; Xiao-Li Chen; Huai-Ming Hu; Hui-Ming Shu; Feng Fu; Meng-Lin Yang; Gang-Lin Xue (143-147).
A new cadmium(II) coordination polymer [Cd2(L)2(bpy)]n·nCH3OH (1) (H2L = 2-(3-oxo-3-phenylpropionyl)-6-pyridinecarboxylic acid N-oxide, bpy = 4,4′-bipyridine), has been synthesized from the reaction of H2L, 4,4′-bipyridine with CdSO4·8/3H2O. Compound 1 is an exceptional non-interpenetrating three-dimensional framework and contains double helical chains and rare cross bpy configuration. Interestingly, these helical chains can span two different directions on other alternate layers. Compound 1 shows intense photoluminescence at room temperature.A new cadmium coordination polymer with new β-diketone-functionalized pyridinecarboxylate and 4,4′-bipyridine ligands shows that an exceptional non-interpenetrating three-dimensional framework contains double helical chains and rare cross bpy configuration and intense photoluminescence at room temperature.Display Omitted
Keywords: Cadmium; β-Diketone derivative; Coordination polymer; Double helical chain; Photoluminescence;

Concerning the chromium precursor CrCl3(THF)3 by Jong Yeob Jeon; Ji Hae Park; Dong Sik Park; Seong Yeon Park; Chun Sun Lee; Min Jeong Go; Junseong Lee; Bun Yeoul Lee (148-150).
The structure of some commercial sources of CrCl3(THF)3 which might be prepared through dehydration of CrCl3·6H2O was discovered to be incorrect. Results of X-ray crystallographic studies showed that the correct structure was CrCl3(H2O)(THF)2. The use of this chromium precursor may have resulted in experimental failures, especially when strongly basic reagents that can deprotonate the coordinated water were reacted. CrCl3(THF)3 prepared through Soxhlet extraction of anhydrous CrCl3 using THF is the correct form of CrCl3(THF)3.The structure of some sources of CrCl3(THF)3 which might be prepared through dehydration of CrCl3·6H2O is the incorrect form of CrCl3(H2O)(THF)2.Display Omitted
Keywords: Chromium precursor; Dehydration; Chromium trichloride; Anhydrous;

Ionothermal synthesis of a new open-framework manganese(II) diphosphate by Yongke He; Yan Yan; Fen Yang; Junbiao Wu; Xiaowei Song (151-154).
A novel open-framework manganese diphosphate compound, [NH3(CH2)2NH3][MnP2O7], denoted as JIS-13 (Jilin Ionothermal Synthesis-13), has been ionothermally synthesized by using a eutectic mixture of tetramethylammonium chloride and 2-imidazolidone as the solvent and template-delivery agent, which in situ yields ethylene diammonium cations (en2+) as the template. The structure of JIS-13 is determined by single-crystal X-ray diffraction and further characterized by powder X-ray diffraction (PXRD), inductively coupled plasma (ICP), thermogravimetric (TG), elemental analyses, X-ray photoelectron spectroscopy (XPS) and magnetic measurements. The alternation of MnO5 trigonal bipyramids and P2O7 units linking through their vertices forms the three-dimensional (3-D) open framework of JIS-13, which comprises 12-ring channels along the [100] direction. Protonated en2+ cations act as the templates to compensate the negative charges of the inorganic framework. Magnetic measurements reveal that weak antiferromagnetic interaction exists in JIS-13.Under ionothermal condition, a novel open-framework manganese diphosphate JIS-13 was synthesized by using a eutectic mixture of tetramethylammonium chloride and 2-imidazolidone as the solvent and template-delivery agent, which in situ yields ethylene diammonium cations (en2+) as the template.Display Omitted
Keywords: Ionothermal synthesis; Open-framework; Manganese diphosphate;

New alkaline earth metal-based coordination polymers with zeolitic ABW, ACO, and chiral (10,3)-a topologies by Maoping Kang; Tingzhi Liu; Xiaohui Wang; Daibing Luo; Ruixiang Li; Zhien Lin (155-158).
A series of alkaline earth metal-based coordination polymers, Mg(ndc)(H2O)·py (1), (Hpy)2·Mg3(ndc)4(H2O)2(py)2 (2), and M(ndc)(dmf) [M = Ca (3), Sr(4), Ba(5)], have been prepared under solvothermal conditions. Compound 1 has a neutral framework with a zeolitic ABW topology. Compound 2 has an anionic framework with a zeolitic ACO topology. Compounds 35 are isostructural and possess a neutral framework with a chiral (10,3)-a topology. The thermal stability, fluorescent properties, and SHG responses of compounds 35 have also been investigated.A series of alkaline earth metal-based coordination polymers have been synthesized. These compounds display different structures with zeolitic ABW, ACO, and chiral (10,3)-a topologies, respectively.Display Omitted
Keywords: Solvothermal synthesis; Open frameworks; Coordination polymer; Alkaline earth metal; Zeolite;

Tetrakis(1-3-diazinane-2-thione)platinum(II) chloride monohydrate complex: Synthesis, spectroscopic characterization, crystal structure and in vitro cytotoxic activity against A549, MCF7, HCT15 and HeLa human cancer lines by A. Zainelabdeen A. Mustafa; Muhammad Altaf; M. Monim-ul-Mehboob; Mohammed Fettouhi; Mohammed I.M. Wazeer; Anvarhusein A. Isab; Vikram Dhuna; Gaurav Bhatia; Kshitija Dhuna (159-163).
This communication reports on the synthesis, crystal structure and anticancer activities of a new Pt(II) complex [Pt(Diaz)4]Cl2  · H2O of a heterocyclic thione, where Diaz = 1,3-diazinane-2-thione. Solid state 195Pt, 15N and 13C NMR are also reported along with other spectroscopic data. The cytotoxic evaluation of the complex against A549, MCF7, HCT15 and HeLa human cancer lines is reported. The title compound was found to be a better cytotoxic agent against MCF7 than cisplatin.This communication reports on the synthesis, crystal structure and anticancer activities of a new Pt(II) complex [Pt(Diaz)4]Cl2  · H2O of heterocyclic thione, where Diaz = 1,3-diazinane-2-thione. Solid state 195Pt, 15N and 13C NMR are also reported along with other spectroscopic techniques. The cytotoxic evaluation against A549, MCF7, HCT15 and HeLa human cancer lines is reported.Display Omitted
Keywords: Dichloridotetrakis(1,3-diazinane-2-thione) platinum(II) complex; Single crystal X-ray structure; 195Pt NMR; In vitro cytotoxicity studies;

Novel Cd(II) bromide complexes [LaCdBr2], [LbCdBr2] and [LcCd(μ-Br)Br]2 have been synthesized and characterized. [LaCdBr2] and [LbCdBr2] were distorted tetrahedral and trigonal bipyramidal geometry around metal, respectively, depending on the coordination of the nitrogen atom of N′-substituted amine moiety and the cadmium center. However, [LcCd(μ-Br)Br]2 reveals a bromo-bridged 6-coordinated dimeric species. Specifically, the catalytic activity of [LbCdBr2] (1.13 × 105  g PMMA/mol Cd·h) in the polymerization of methyl methacrylate (MMA) in the presence of modified methylaluminoxane (MMAO) at 60 °C was higher than that of [LaCdBr2] (5.03 × 104  g PMMA/mol Cd·h) and reference complex [CdCl2] (3.53 × 104  g PMMA/mol Cd·h).Novel Cd(II) bromide complexes [LaCdBr2], [LbCdBr2], and [LcCd(µ–Br)Br]2 have been synthesized. [LaCdBr2] and [LbCdBr2] were distorted tetrahedral and trigonal bipyramidal geometry around metal, respectively, depending on the coordination of the nitrogen atom of N’-substituted amine moiety and the cadmium center. However, [LcCd(µ–Br)Br]2 reveals a bromo-bridged 6-coordinated dimeric species.Display Omitted
Keywords: Bispyrazolyl; Dimeric Cd(II) complex; Methyl methacrylate polymerization; Syndiotacticity;

Two indium sulfides [(Me)4N]6[In10S18] (1) and [(Me)4N]13[Cu5In30S54] (2) have been hydrothermally synthesized. Compound 1 is a 3D open framework built from T3 clusters, which has large porosity. Compound 2 has a double-layered structure constructed by T5 clusters. Our results indicate that tetramethylammonium ion is an efficient structure-directing agent for both ternary and quaternary indium sulfides. The optical and thermal properties have also been investigated.Two indium sulfides have been hydrothermally synthesized in the presence of tetramethylammonium ion as structure-directing agent.Display Omitted
Keywords: Hydrothermal synthesis; Indium sulfide; Template effect; Crystal structure;

Cu2 +-templated self-assembly of an asymmetric Salen–Cu(II) complex and its application in catalytic polymerization of methyl methacrylate (MMA) by Liqin Ding; Shengrong Liang; Juntao Zhang; Changfeng Ding; Yan Chen; Xingqiang Lü (173-176).
With the mono-imine HL (HL  = (E)-2-((2-aminophenylimino)methyl)-4,6-di-tert-butyl-phenol) as the precursor, an asymmetric Salen-type Schiff-base complex [Cu(L2)] (3, H2L2  = 2-((E)-2-((E)-2-hydroxybenzylideneamino)phenylimino)methyl-4,6-di-tert-butylphenol) was obtained by Cu2 +-templated approach in the presence of salicylaldehyde due to the formation of intermediate {[Cu(L)(OAc)]}2 (2)2. In contrast to the inertness for 2/AIBN system (AIBN = azobis(isobutyronitrile)), both the symmetric and asymmetric Salen-type Schiff-base complexes [Cu(L1)] (1, H2L1  = N, N′-bis(3,5-di-tert-butyl-salicylidene)phenylene-1,2-diamine) and [Cu(L2)] (3) as the catalysts in the presence of AIBN could effectively catalyze the solution polymerization of MMA (MMA = methyl methacrylate) for the formation of the syndio-enriched PMMAs, where the steric and the electronic effects of the ligands play an important and influential role on the catalytic behaviors, while on the premise of controllable polymerizations the variation of polymerization conditions almost has no effect on the polymer tacticity.An asymmetric Salen-type Schiff-base complex [Cu(L2)] (3, H2L2  = 2-((E)-2-((E)-2-hydroxybenzylideneamino)phenylimino)methyl-4,6-di-tert-butylphenol) was obtained by Cu2+-templated approach due to the formation of intermediate {[Cu(L)(OAc)]}2 (2)2. In contrast to the inertness for 2/AIBN system (AIBN = azobis(isobutyronitrile)), both [Cu(L1)] (1, H2L1  = N, N’′-bis(3,5-di-tert-butyl-salicylidene)phenylene-1,2-diamine) and 3 could effectively catalyze the polymerization of MMA (MMA = methyl methacrylate) for the formation of the syndio-enriched PMMAs.Display Omitted
Keywords: Cu2 +-templated self-assembly; Asymmetric or symmetric Salen-type Schiff base; Syndio-enriched atactic PMMA; Steric and electronic effects;

Synthesis, characterization and reactivity of a novel Di-nickel complex towards carbon dioxide by William Seals; Hadi Arman; Stephan B.H. Bach; Ghezai T. Musie (177-179).
Newly synthesized dinickel complex 1, K2[Ni2(ccdp)(C5H7O2)(H2O)2], reacts with CO2 to produce a novel bis(μ-η 2,η 2)-carbonato bridged tetranickel complex 2, Cs6[Ni4(ccdp)2(μ-η 2-η 2-CO3)2], via an intermediate species that contains a bis(μ-OH) dinickel(II) moiety, complex 3.Display Omitted
Keywords: Carbon dioxide; Nickel complex; Carbonato ligand; Metal complex activation;

Synthesis and structural characterisation of a new tantalum hydroxylamide dimer by Hywel O. Davies; Benjamin Peek; Jennifer Rochford; Paul O'Brien; Mohammad Afzaal; Christopher Murin; Craig P. Dawson (180-182).
The first structurally characterised tantalum(V) diethylhydroxylamide, [Ta(= O)(ONEt2)3]2, is reported. Structural analysis reveals a dimer with bridging oxygen atoms and η2-O,N chelated hydroxylamido ligands.The first structurally characterised tantalum(V) diethylhydroxylamide, [Ta(=O)(ONEt2)3]2, is reported. Structural analysis reveals a dimer with bridging oxygen atoms and η2-O,N chelated hydroxylamido ligands.Display Omitted
Keywords: Tantalum(V); Diethylhydroxylamide; MOCVD; Dimer; Crystallography;

Towards the clathrochelate-based electrochromic materials: The case study of the first iron(II) cage complex with an annelated quinoxaline fragment by Alexey B. Burdukov; Mikhail A. Vershinin; Natalie V. Pervukhina; Evgenii G. Boguslvaskii; Ilia V. Eltsov; Leonid A. Shundrin; Sofia L. Selector; Alexander V. Shokurov; Yan Z. Voloshin (183-187).
Nucleophilic substitution of the bis-α-benzyldioximate clathrochelate precursor with ortho-phenylenediamine hydrochloride in the presence of triethylamine as an organic base under mild conditions afforded the macrobicyclic iron(II) complex with an annelated ribbed quinoxaline fragment. This complex easily underwent oxidation in solution with air oxygen leading to its oxidized macrobicyclic derivative with the quinoid ribbed system. Such cage complex with a heterocyclic fragment annelated to its quasi-aromatic polyazomethine electron-withdrawing macrobicyclic framework possesses pronounced oxidative properties and undergoes both the chemical (with metallic lithium) and electrochemical stepwise reduction to the corresponding radical anion macrobicyclic species, registered by EPR, and, then, to the diamagnetic dianionic clathrochelate complex. Such reductions were found to be accompanied by dramatic changes in coloration from blue–violet to yellow (that is characteristic of the macrobicyclic anion radical) and orange–red (that is characteristic of the clathrochelate dianion); these redox and electrochromic properties were studied using cyclic voltammetry and spectroelectrochemistry in solution and in a thin film. The clathrochelates obtained were characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV–vis, EPR, 1H, 11B, 19F and 13C{1H} NMR spectroscopy, and by X-ray diffraction; their FeN6 -coordination polyhedra possess a distorted trigonal prismatic–trigonal antiprismatic geometry with the distortion angles of approximately 24°. The Fe–N distances vary from 1.89 to 1.94 Å, and the heights h of such polyhedra are 2.33 and 2.36 Å, respectively. So, the first clathrochelates with redox-innocent encapsulated metal ion and redox-active macrobicycle ligand systems have been prepared and characterized. For the first time, a quasi-aromatic polyazomethine cage metal complex with an annelated redox-active heterocyclic fragment, having an extended π-conjugated system, has been shown to undergo a reversible 2-electron reduction accompanied with electrochromism both in solution and as a thin film.Nucleophilic substitution of a dichloroclathrochelate precursor with ortho-phenylenediamine and further chemical oxidation of the macrobicyclic product gave the iron(II) clathrochelates with annelated quinoxaline and diaminophenylene ribbed fragments; the former exhibits electrochromism both in solution and in a thin film.Display Omitted
Keywords: Macrocyclic compounds; Clathrochelates; Iron complexes; Ligand reactivity; Electrochromism;

A new penta-carboxylate and N-donor ligand co-regulate 3D CoII-MOF with tcj/hc topology: Synthesis, structure and magnetic property by Liang Bai; Hai-Bing Wang; Dong-Sheng Li; Ya-Pan Wu; Jun Zhao; Lu-Fang Ma (188-190).
A 3D CoII metal-organic framework, {[Co4(Hbpbc)2(4,4′-bipy)(H2O)4]·3H2O} n (1), based on a new penta-carboxylate(H5bpbc = biphenyl-2,4,6,3′,5′-pentacarboxylic acid) and 4,4′-bipyridine is presented. In 1, each μ 7-Hbpbc4 − anion links five [Co2] SBUs to generate a 3D 5-connected noy net. Further, 4,4′-bipy ligands compensate for the need of Co2 coordination to regulate noy net into a 3D (5,6)-connected tcj/hc framework. Besides, the thermal stability and magnetic property of 1 were also investigated.A 3D Co metal-organic framework based on a new penta-carboxylate and 4,4′-bipyridyl is presented, which possesses a rare (5, 6)-connected tcj/hc network topology and shows dominant antiferromagnetic properties.Display Omitted
Keywords: CoII metal-organic framework; Crystal structure; Topology; Biphenyl-2,4,6,3′,5′-pentacarboxylic acid; Magnetic property;

The first 2-D organic–inorganic hybrid containing two types of hexa-CuII sandwiched polyoxotungstate units and mixed amines by Rui-Qin Li; Yan-Ying Li; Bai-Feng Yang; Huan He; Jun-Wei Zhao; Guo-Yu Yang (191-194).
A novel 2-D hexa-CuII substituted sandwich-type polyoxotungstate [Cu(H2O)4][Cu(dien)(H2O)2]2[Cu(dien)(H2O)]2[Cu6(en)2(H2O)2(B-α-HGeW9O34)2][Cu6(Hdien)2(H2O)2(B-α-HGeW9O34)2]·24 H2O (1, en = ethylenediamine, dien = diethylenetriamine) has been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and single-crystal X-ray diffraction. 1 represents the first 2-D inorganic–organic hybrid sandwich-type germanotungstate constructed by two kinds of hexa-CuII substituted sandwich-type POM hybrid units accompanying the mixed organoamine components in the structure. The TGA curve of 1 displays two continuous weight loss stages.A novel polyoxotungstate was made and characterized, in which two kinds of hexa-Cu sandwiched polyoxoanions, [Cu6(en)2(H2O)2(B-α-HGeW9O34)2] and [Cu6(Hdien)2(H2O)2(B-α-HGeW9O34)2], linked by [Cu(dien)(H2O)]2 + and [Cu(H2O)4]2 + complex bridges to form 2-D layer.Display Omitted
Keywords: Polyoxometalate; Hydrothermal synthesis; Sandwich-type structure; Mixed amines;

Self-assembly and photocatalytic hydrogen evolution of a niobium-containing polyoxometalate by Zhao-Xia Yang; Peng Huang; Liang Zhao; Min Zhang; Yu-Teng Zhang; Zhong-Min Su (195-197).
A tetra-Keggin polyoxometalate (POM), Cs19K2[Nb4O6(SiW9Nb3O40)4]Cl·27H2O (1) with a photocatalytic property has been synthesized by utilizing the self-assembly of W/Nb mixed-addendum POM [SiW9(NbO2)3O37]7 − under hydrothermal conditions. Its structure was determined by single-crystal X-ray diffraction, and further characterized by IR spectroscopy, thermogravimetric analysis, and cyclic voltammetry. Moreover, the photocatalytic activity of 1 for H2 evolution from water was observed under UV irradiation, suggesting that 1 might be a promising photocatalytic catalyst.Compound 1 was obtained by the aggregation of niobium under hydrothermal conditions. 1 may be depicted as four {SiW9O34} units linked together by a {Nb16O30} cluster. Moreover, the photocatalytic activity of 1 for H2 evolution from water was observed under UV irradiation.Display Omitted
Keywords: Polyoxometalate; Niobium; Self-assembly; Photocatalytic property;

Self-assembled microporous lanthanide coordination polymers built by 2-hydroxynicotinic acid and oxalate ligands by Xingmei Guo; Yingxin Gong; Xiaoting Huang; Yuanyuan Tian; Yanlin Zhang; Shengrun Zheng; Ronghua Zeng; Mengqing Xu (198-201).
Two new microporous lanthanide coordination polymers, namely, [Eu(Hnica)2(ox)2(H2O)2] · 5H2O (1) and [Gd(Hnica)2(ox)2(H2O)2] · 5H2O (2), have been successfully synthesized by reaction of 2-hydroxynicotinic acid (H2nica) in the presence of the coligand oxalate (ox) with lanthanide ions under hydrothermal conditions. Single crystal X-ray diffraction analyses reveal that compounds 1 and 2 are isostructural and exhibit two-dimensional (2D) layer architectures built by the linkage of 1D Ln–ox chains with μ 2- Hnica bridging ligands, which are further connected by strong π–π stacking interactions to form 3D microporous supramolecular frameworks. Furthermore, the thermal stability and solid-state luminescent behavior of compound 1 were also investigated.Space-filling diagram of the 3D porous supramolecular framework of two rare lanthanide coordination polymers formed via the strong interlayer π⋯π stacking interactions is studied.Display Omitted
Keywords: Hydrothermal synthesis; 2-Hydroxynicotinic acid; Lanthanide coordination polymers; Microporous;