Inorganic Chemistry Communications (v.31, #C)

Contents List (iii-viii).

A novel coordination complex {[Cu14(pytz)8(CN)10(H2O)2]·H2O} n (1, Hpytz = 5-(2-pyridyl)-2H-tetrazole) has been synthesized by the hydrothermal reaction of Cu(NO3)2 with Hpytz ligand in mixed CH3CN/H2O solution under 150 °C. The cyanide may be generated in situ from the C–C cleavage of acetonitrile under hydrothermal conditions. Complex 1 consists of an infinite 2D network with CN and pytz ligand bridges. Magnetic susceptibility measurement indicates that 1 shows antiferromagnetic interaction between the adjacent Cu(II) ions.This paper describes the unprecedented preparation of unique 2D multinuclear copper based metal-tetrazolate networks by in situ solvothermal reaction under 150 °C. Magnetic susceptibility measurement indicates that 1 shows antiferromagnetic interaction between the adjacent Cu(II) ions.Display Omitted► A novel 2D multinuclear copper polymer 1 has been synthesized. ► CuII ions have different coordinated modes. ► The cyanide should be generated in situ from the C–C cleavage of acetonitrile. ► 1 shows antiferromagnetic interaction.
Keywords: Multinuclear copper; In-situ reaction; Magnetic property;

Effect of lanthanide contraction on structures of 3D lanthanide organic frameworks from 5-nitroisophthalic acid and picolinic acid by Jin-Ying Gao; Xia-Hua Xiong; Chu-Jun Chen; Wei-Ping Xie; Xing-Rui Ran; Shan-Tang Yue; Ying-Liang Liu; Yue-Peng Cai (5-12).
Two different types of novel lanthanide coordination polymers constructed from 5-nitroisophthalic acid, and picolinic acid as auxiliary ligand, namely, {[Ln2(nip)2(pic)2(H2O)]}n (type I, Ln = Pr 1, Nd 2, Sm 3, Eu 4, and H2nip = 5-nitroisophthalic acid, Hpic = picolinic acid), and {[Ln4(nip)5(pic)2(H2O)2]·2H2O}n (type II, Ln = Tb 5, Dy 6, Ho 7, Er 8), have been hydrothermally synthesized and characterized by IR, elemental analysis, thermogravimetric analysis (TGA), single-crystal X-ray diffraction analyses and powder X-ray diffraction (PXRD). Complexes 14 (type I) are isostructural and the infinite 1D Sm-carboxylate chains are bridged by pia ligands to form 2D sheets, such sheets are further united together to generate a 3D supramolecular structure. Complexes 58 (type II) are isostructural and the infinite 1D Tb–carboxylate chains are bridged by pia ligands to form 2D sheets, such sheets are further united together to generate a 3D supramolecular structure. Furthermore, the luminescence properties of compounds 4 and 5 have also been studied.The coordination modes of H2nip and Hpic ligands.Display Omitted► Two different types of novel lanthanide coordination polymers have been synthesized. ► Lanthanide contraction affects the structure of eight complexes. ► Complexes 4 and 5 exhibit characteristic lanthanide-centered luminescence.
Keywords: Hydrothermal synthesis; Lanthanide ion; Topology; Luminescence;

Metal ion-driven assembly of 3D coordination polymers with 5-oxyacetate isophthalic acid and 4,4′-bis(1-imidazolyl)bibenzene by Hong-Jian Cheng; Bing Wu; Lian-Wen Zhu; Chun-Yan Ni; Ming Dai; Hong-Xi Li; Zhi-Gang Ren; Jian-Ping Lang (13-17).
Hydrothermal reactions of NiCl2·6H2O or CdCl2·2.5H2O with 4,4′-bis(1-imidazolyl)bibenzene (bimb) and 5-oxyacetate isophthalic acid (H3OAIP) resulted in the formation of two coordination polymers [Ni2(HOAIP)2(bimb)3(H2O)2] n (1) and [Cd3(OAIP)2(bimb)(H2O)2] n ·2nH2O (2), respectively. Compounds 1 and 2 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. 1 exhibits three-fold interpenetrating 3D architecture with a (44  · 65  · 8) Schläfli symbol in which 1D [Ni(HOAIP)] n chains are interlinked by bimb ligands. In 2, the two [Cd2(OAIP)4] and [Cd2(OAIP)4(H2O)4] units are interconnected by OAIP and bimb to afford a 3D network with a unique (4 · 82)4(42  · 68  · 85)2(86) Schläfli symbol. The results showed that metal ions did exert great influence upon the coordination modes and the geometrical conformations of ligands and the topological structures of the final products. Their thermal and photoluminescent properties were also investigated.Two 3D coordination polymers [Ni2(HOAIP)2(bimb)3(H2O)2] n and [Cd3(OAIP)2(bimb)(H2O)2] n ·2nH2O were generated from solvothermal reactions of NiCl2·6H2O or CdCl2·2.5H2O with 4,4′-bis(1-imidazolyl)bibenzene (bimb) and 5-oxyacetate isophthalic acid (H3OAIP). Both complexes were structurally characterized by elemental analysis, IR, and X-ray crystallography and their thermal and luminescent properties were studied.Display Omitted► Solvothermal reactions of NiCl2 or CdCl2 with bimb and H3OAIP gave two complexes. ► Compound 1 holds a unique three-fold interpenetrated 3D architecture. ► Compound 2 has a 3D net containing [Cd2(OAIP)4] and [Cd2(OAIP)4(H2O)4] units. ► It offers insight into how the resulting architecture is affected by metal ions.
Keywords: Nickel(II) coordination polymer; Cadmium(II) coordination polymer; 5-Oxyacetate isophthalic acid; 4,4′-Bis(1-imidazolyl)bibenzene; Hydrothermal reactions; Crystal structures;

A 2-D cobalt–organic framework formulated as [Co(bdc)(bptb)]n (1), built from a mixed 1,2-benzenedicarboxylate anion (bdc), 1,4-bis(5-(4-pyridyl)-1H-1,2,4-triazol-3-yl)benzene (bptb), and cobalt salt, has been hydrothermally synthesized and characterized. Complex 1 has a [Co(bdc)]n chain structure in which the chains are isolated by the bptb ligands in a 2-D wave-like architecture. The magnetic behavior of complex 1 was studied, and it indicated the coexistence of spin-canted weak ferromagnetism with TN  = 10 K and long-range magnetic ordering.In this paper, a 2-D Cobalt-organic framework formulated as [Co(bdc)(bptb)]n (1), built from a mixed 1,2-benzenedicarboxylate anion (bdc), 1,4-bis(5-(4-pyridyl)-1H-1,2,4-triazol-3-yl)benzene (bptb), and cobalt salt, has been hydrothermally synthesized and characterized. Complex 1 indicated the coexistence of spin-canted weak ferromagnetism with TN  = 10 K and long-range magnetic ordering.Display Omitted► A 2-D coordination polymers with new mixed-ligand system have been synthesized. ► Complex 1 indicated spin-canted weak ferromagnetism with TN  = 10 K, and long-range magnetic ordering. ► Bptb is a long bent linker.
Keywords: Crystal structures; Bent ligand; Spin canting;

Solvothermal reactions of 4-cyanobenzoic acid (HL1 ), NaN3, hydrated ZnSO4 in the presence of ancillary ligands pyrazine or 4,4′-dimethylbipyridine (Me2bpy) afforded a 3-D coordination polymer [Zn(L2 )(H2O)]n (1) and a 2-D layer [Zn3(Me2bpy)(N3)2(L2 )]n (2) (L2  = 4-tetrazolylbenzenecarboxylate), respectively in which pyrazine significantly alters the self-assembly of 1 and the coordination of Me2bpy in 2 leads to a novel linearly trinuclear [Zn3(Me2bpy)2(N3)2]4 + subunit functioning as a secondary building block (SUB). Their crystal structures have been determined by X-ray crystallography and solid state luminescent properties have been measured at room temperature.Solvothermal reactions of 4-cyanobenzoic acid (HL1), NaN3, hydrated ZnSO4 in the presence of pyrazine or 4,4-dimethylbipyridine (Me2bpy) afforded complexes [Zn(L2)(H2O)]n (1) and [Zn3(Me2bpy)(N3)2(L2)]n (2), respectively in which pyrazine alters the self-assembly of 1 and the coordination of Me2bpy in 2 leads to a linearly trinuclear [Zn3(Me2bpy)2(N3)2]4+ subunit as a SUB.Display Omitted► Pyrazine significantly alters the self-assembly of 1 ► The novel [Zn3(Me2bpy)2(N3)2]4+ cores functions as the SUBs in 2 ► A 44 grid topological architecture with grid length of 12.5 Å in 2 is generated ► The luminescence properties have been measured.
Keywords: Zinc(II); Tetrazole; Ancillary ligand; Luminescence;

Length tunable porphyrinoid porous coordination polymer rods and their heterogeneous catalytic study on olefin oxidation by Sundol Kim; Young Sun Lee; Da Hee Lee; Min Young Hyun; Jin-Yeon Hong; Seong Huh; Cheal Kim; Suk Joong Lee (29-32).
We developed a series of micro-size hexagon-faced plate and rods from Mn(III)-porphyrin and In(III) whose lengths were modulated by water. Regardless of a wide range of length distribution, they are isostructural. In addition, the heterogeneous olefin oxidation was performed.The modulation of Mn(III)-porphyrin based micro-sized porous coordination polymers (PCPs) from hexagonal plate to rods has been demonstrated. Regardless of a wide range of length distribution, they are isostructural. Furthermore, the oxidation of various olefins has been successfully demonstrated with Mn(III)-porphyrin based PCPs.Display Omitted
Keywords: Coordination polymer; Metal–organic frameworks; Isostructural; Heterogeneous; Oxidation;

Solvothermal syntheses and crystal structures of one 1D and two 3D [PbxIy]-based coordination polymers by Zhen-Jun Huang; Hong-Jian Cheng; Ming Dai; Chun-Yan Ni; Hong-Xi Li; Kai-Peng Hou; Zhi-Gang Ren; Jian-Ping Lang (33-36).
Reactions of PbI2 with KI, I2 and 1,2-bis(diphenylphosphino)ethane (dppe) (molar ratio = 1:5:3:4) in MeCN/EtOH under solvothermal conditions afforded a one-dimensional (1D) coordination polymer [(EP)(Pb2I6)]n (EP2 +  = ethane-1,2-diylbis(ethyldiphenylphosphonium)) (1) and a three-dimensional (3D) coordination polymer [{(Pb3(μ-I)6)(dppeo)3}·EtOH]n (2) (by-product). Treatment of the same components with H2O2 under similar conditions produced another 3D coordination polymer [{Pb2(μ-I)23-I)2}(dppeo)]n (dppeo = ethane-1,2-diylbis(diphenylphosphine oxide)) (3). Compound 2 could also be prepared in a medium yield from solvothermal reactions of PbI2 with KI, I2 and dppeo (molar ratio = 1:5:3:4). Compounds 13 were characterized by elemental analysis, IR and single crystal X-ray diffraction. Compound 1 contains one 1D anionic [PbI3]n n − chain with EP2 + dications being embedded between chains. The EP2 + dication was in situ generated via the cleavage of C―O bond of EtOH followed by alkylation of dppe. Compound 2 consists of trinuclear [Pb3(μ-I)6] fragments that are interlinked via dppeo bridges to form a 3D 6-connected net (a 41263 Schläfli symbol). Compound 3 has a 3D net (with a 66 Schläfli symbol) constructed from 1D [Pb2(μ-I)23-I)2]n chains linked by dppeo ligands. The dppeo ligand in 3 was formed in situ from the oxidation of dppe by H2O2. The optoelectronic properties of 13 were also investigated.Reactions of 1,2-bis(diphenylphosphino)ethane (dppe) with PbI2, KI and I2 under solvothermal conditions afforded one 1D anionic polymer [(EP)(Pb2I6)]n and one 3D polymer [{(Pb3(μ-I)6)(dppeo)3} · EtOH]n. Analogous reactions of PbI2 with KI, I2 and dppeo generated another 3D polymer [{Pb2(μ-I)23-I)2}(dppeo)]n. The three complexes were structurally characterized and their optoelectronic properties were studied.Display Omitted
Keywords: Solvothermal synthesis; Iodoplumbate; Optoelectronic property; Crystal structure; Ethane-1,2-diylbis(diphenylphosphine oxide); Ethane-1,2-diylbis(ethyldiphenylphosphonium);

A new ligand 1-(pyridin-2-ylmethyl)-2-(3-(1-(pyridin-2-ylmethyl)benzimidazol-2-yl) propyl) benzimidazole (L) and its Cu(II) complex (1) have been synthesized and characterized spectroscopically and structurally. The Cu(II) ion is coordinated by two nitrogen atoms of benzimidazole groups, two oxygen atoms of the nitrate anions and one oxygen atom of a water molecule forming distorted trigonal bipyramidal geometry. The ligand and its complex have been utilized as a fluorescent sensor for 4-(2-aminoethyl)benzene-1,2-diol. A plot of F0/F − F0 vs 1/Conc (4-(2-aminoethyl)benzene-1,2-diol) at a selected wavelength of 306 nm with (L) that shows a straight line behavior, supports the validity of the assumption of 1:1 complex formation and the association constant of (L) with 4-(2-aminoethyl)benzene-1,2-diol is calculated to be 9868 M− 1. Sensor (L) is found to be selective for 4-(2-aminoethyl)benzene-1,2-diol over aromatic amines, phenols, amino catechol (L-3,4-dihydroxyphenylalanine) and 4,6-ditertiarybutyl benzene-1,2-diol.A new ligand N-picolylated bis-benzimidazolyl ligand (L) and its copper(II) complex have been synthesized, characterized spectroscopically and structurally. The geometry of Cu(II) is distorted in trigonal bipyramidal. The ligand and the complex have been utilized as a florescent sensor for dopamine. A new band generated with ligand is due to the formation of a host guest complex formed between pyridine moiety and dopamine. Sensor (L) is selective to the compounds bearing both the amino and phenolic moiety, as is the case with dopamine.Display Omitted► New bis benzimidazole ligand has been synthesized and characterized structurally. ► Cu (II) complex of the ligand has been synthesized and characterized structurally. ► The ligand and its complex have been utilized as a fluorescent sensor for dopamine. ► Ligand is found to be selective for dopamine over aromatic amines and phenols.
Keywords: Benzimidazole; Copper complex; Structure; Fluorescent sensor;

Based on 4-substituted mono- and bis-triazole ligands 4-2-pyridyl-1,2,4-triazole (L1) and 2,6-(1,2,4-triazole-4-yl)-pyridine (L2), a series of iron(II)-triazole complexes, namely [Fe22-L1)3(L1)2(NCS)4] 2H2O (1), [Fe22-L1)3(L1)2(NCS)4] CH3OH CH3CH2OH (2) and [Fe(μ2-L2)2(NCS)2]n (3) have been isolated. For the Fe(II)-L1 system, though dinuclear complexes were obtained in both aqueous solution and methanol/ethanol solution for 1 and 2, respectively, anti-ferromagnetic interactions were found in 1 while incomplete spin transition phenomenon was found in 2. Low temperature structural analysis (100 K) of 2 is consistent with one of the Fe(II) centers within the dinuclear complex at low spin (LS) state and the other at high-spin (HS) state resulting in a [LS:HS] species. When L2 is used under the similar preparation method for 12, one-dimensional neutral iron (II) chain complex 3 is isolated. The different substituted groups and solvent effect are both important for self-assembly and different magnetic properties of these crystalline iron(II)-triazole complexes 13.A series of iron(II)-triazole complexes have been isolated. Incomplete spin transition phenomenon was found in 2. The different substituted groups and solvent effect are both important for self-assembly and magnetic properties of these crystalline iron(II)-triazole complexes.Display Omitted
Keywords: Fe(II); Spin transition; Solvent effect; Neutral iron(II) chain;

Three new coordination polymers, [Co(HBit)2]n (1), [Mn(HBit)2]n (2) (H2Bit = 2-((1H-tetrazol-5-yl)methyl)-1H-benzo[d]imidazole), and [CdCl(MBi)(HMBi)]n (3), (HMBi = 2-methyl-1H-benzo-[d]imidazole), have been hydrothermally synthesized via in situ ligand reaction. Compounds 1 and 2 are isomorphous and display interesting 3D chiral supramolecular frameworks constructed from one-dimensional 41 helical chains. Complex 3 possesses a one-dimensional coordination chain, which is further connected to a 2D layer by intermolecular hydrogen bonds. More interestingly, both H2Bit and HMBi ligands are in situ generated from the same precursor, 2-(1H-benzo[d]imidazol-2-yl)-acetonitrile, and the formation may depend on the kind of metal ion. Furthermore, the solid-state luminescence of complex 3 was investigated at room temperature.Three new coordination polymers were obtained by using in situ reaction from the same precursor.Display Omitted
Keywords: In situ reaction; Chiral; 2-((1H-tetrazol-5-yl)methyl)-1H-benzo[d]imidazole; Supramolecular framework;

From the reaction of AgCC t Bu with 9-hydroxy-9-fluorenecarboxylic acid (HL) and AgCF3CO2, we have isolated a new type of organosilver(I) coordination polymeric chain, namely {[Ag14(CC t Bu)8(L)2(CF3CO2)4]·2CH3OH} n , which contains centrosymmetric [Ag14(CC t Bu)8(CF3CO2)2]4 + cluster segments bridged by pairs of L and trifluoroacetate ligands.The crystalline silver(I)–ethynide complex {[Ag14(CC t Bu)8(L)2(CF3CO2)4]·2CH3OH} n (HL = 9-hydroxy-9-fluorenecarboxylic acid) is composed of a packing of organosilver(I) coordination polymeric chains each containing centrosymmetric, bar-like [Ag14(CC t Bu)8(CF3CO2)2]4 + cluster segments bridged by pairs of L and trifluoroacetate ligands.Display Omitted
Keywords: Metal–ligand supramolecular synthon; Organosilver complex; Polymeric coordination chain; Silver(I) ethynide cluster;

A cyanide-bridged two-dimensional grid-like FeIII–CoII complex based on the pentacyanideferrite(III) building block by Guo-Ling Li; Zhong-Hai Ni; Wei-Qin Cheng; Bao-Xi Miao; Li-Fang Zhang (58-61).
A cyanide-bridged FeIII–CoII heterometallic complex {[Fe(1-CH3im)(CN)5][Co(H2O)2]}n·3H2O (1-CH3im = 1-methylimadazole) (2) has been synthesized by the reaction of CoII(ClO4)2·6H2O with the pentacyanideferrite(III) building block (Ph4P)2[FeIII(1-CH3im)(CN)5]·4.5H2O (1). X-Ray single crystal diffraction analysis shows that complex 2 has a two-dimensional (2D) grid-like structure. Magnetic investigations show that complex 2 displays long-range antiferromagnetic ordering with T N  = 9.45 K. The typical metamagnetic behaviors were observed with the critical field of ca. 4000 Oe at 1.82 K.A new cyanide-bridged two-dimensional grid-like binuclear FeIII–CoII complex {[Fe(1-CH3im)(CN)5]-[Co(H2O)2]}n·3H2O (1-CH3im = 1-methylimadazole) (2) based on the pentacyanideferrite(III) building block (Ph4P)2[FeIII(1-CH3im)(CN)5]·4.5H2O (1) has been synthesized. The crystal structures and magnetic properties of complexes 1 and 2 have been investigated in detail.Display Omitted
Keywords: Cyanide-bridged; Heterometallic; Grid-like structure; Magnetic properties;

A three-dimensional (3D) metal-organic framework having a unique tetradecanuclear {Zn12(μ 3-OH)6Na2(μ 2-O)}18 + hetero-metal cluster core, formulated as {Zn12(BTDA)9(μ 3-OH)6Na2(μ 2-O)} (1) [H2BTDA = 4,4'-(4,4'-dibutyl-2,2'-bithiazole-5,5'-diyl)dibenzoic acid], has been described herein. The tetradecanuclear hetero-metal cluster core is composed of two heptanuclear {Zn6(μ 3-OH)3Na}10 + trifolium-shaped subunits where the axle sodium(I) ion is connected with three pairs of zinc(II) ions by three μ 3-OH ions and the two sodium(I) ions are further linked by a μ 2–oxo bridge. Besides, the auxiliary BTDA ligand serves as a multi-dentate bridging mode linking adjacent tetradecanuclear hetero-metal clusters into a 3D coordination polymer where a rhombohedral array with a new (418  · 8108  · 1227) · (4)9 topology is observed.A three-dimensional pcu-type supramolecular framework, bearing a tetradecanuclear {Zn12(μ 3-OH)6Na2(μ 2-O)}18 + hetero-metal cluster core and two heptanuclear {Zn6(μ 3-OH)3Na}10 + trifolium-shaped subunits, is obtained in the presence of an auxiliary bithiazole dibenzoate ligand.Display Omitted
Keywords: Hetero-metal cluster; Sodium(I) template; Zinc(II) complex; Crystal structure; Fluorescence spectrum;

Structure and enhanced piezoelectric response by chemical doping in PbTiO3–PbZrO3–Bi(Ni1/2Ti1/2)O3 by Huajun Kang; Jun Chen; Laijun Liu; Changzheng Hu; Liang Fang; Xianran Xing (66-68).
The piezoelectric ceramics (1 −  x  −  y)PbTiO3  −  xPbZrO3  −  yBi(Ni1/2Ti1/2)O3 exhibit greatly enhanced piezoelectric properties at morphotropic phase boundaries (MPB). X-Ray diffraction (XRD) analysis was used to investigate the MPB structure of (1 −  x  −  y)PbTiO3  −  xPbZrO3  −  yBi(Ni1/2Ti1/2)O3 ceramics. The dielectric, ferroelectric, and piezoelectric properties were systematically investigated. The morphotropic phase boundaries are at x  = 0.10, 0.20, 25; y  = 0.46, 0.39, 0.34, respectively. An optimum high temperature piezoelectric ceramic is obtained at the composition of x  = 0.20 and y  = 0.39 (d 33  = 510 pC/N, d 33(bi) = 462 pm/V, Tc  = 318 °C, Ec  = 20.0 kV/cm and Pr  = 25.5 μC/cm2).P–E hysteresis loops of PZ10–BNT46–PT, PZ20–BNT39–PT and PZ25–BNT34–PT; S–E bipolar loops of PZ10–BNT46–PT, PZ20–BNT39–PT and PZ25–BNT34–PT.Display Omitted
Keywords: Ceramics; Ferroelectricity; Piezoelectricity; PT–PZ–BNT;

Density functional theory (DFT) and time-dependent density functional theory (TDDFT) were employed to study the solvent dependent luminescence of metal–organic framework (MOF) Cu4(L)4•2EtOH (L  = 5-(4-pyridyl) tetrazole). The truncated representative fragment of Cu4(L)4•2EtOH 1 and its solvated form 2 in ethanol were employed for the computation. The structures of 1 and 2 in S0, S1 and T1 states were fully optimized. Based on our frontier molecular orbital and the electronic configuration analysis of the optimized ground state structures of 1 and 2, the ligand-to-metal charge transfer (LMCT) luminescence was confirmed and the charge transfer pathway during the luminescent process was proved to be elongated by the hydrogen bond which led to the luminescence enhancing effect. Besides, the strengthening of hydrogen bond in S1 and T1 states, proved by our TDDFT calculation, enlarged the HOMO-LUMO energy gap which inhibited non-radiative decay thus in favor of luminescence. Particularly, the behaviors of coordination bonds in S1 and T1 states were investigated. The weakening of hydrogen bond greatly strengthened the coordination bond Cu1―N1 in S1 and T1 states. The strengthening of this coordination bond confined the charge transfer from Cu1 to Cu2 which further enhanced the luminescence.The electronic configurations and frontier molecular orbitals of MOF Cu4(L)4•2EtOH were calculated. The results showed that the luminescent of this framework originated from ligand to metal charge transfer (LMCT).Display Omitted
Keywords: Metal–organic frameworks; Luminescence; Time-dependent density functional theory; Hydrogen bond; Coordination bond;

Synthesis, structure and reactivity of NHC–nickel complexes containing carbonato ligands by Jin Guo; Lanlan Lv; Xiaojun Wang; Changsheng Cao; Guangsheng Pang; Yanhui Shi (74-78).
Reactions of different alkane-bridged (n  = 1–3) di-NHC precursors, bisimidazolium chlorides with the NiCl2 in presents of K2CO3 in acetonitrile give the corresponding 16-electron binuclear complexes of the type Ni(di-NHC)(μ-O)2CO in moderate yield. The molecular structures of 13 have been determined by X-ray crystallography, which revealed a cis-chelating di-NHC on a slightly distorted square-planar nickel center with κ2-cabonato ligand. The influence of the different di-NHC ligands on the structure and reactivity of the complexes has been studied. The catalytic properties of the complexes were investigated in the Kumada reaction for cross-coupling of phenylmagnesium bromide with a variety of aryl halides. The complex 3 which has the longest linker between two NHCs shows the best catalytic activity in these reactions.A series of novel cis-chelating di-NHC nickel complexes containing carbonato ligands have been synthesized. The molecular structures have been determined. The nickel center is surrounded by di-NHC and κ2-catonato ligand on a slightly distorted square plane. The length of linker has effect on the structures and catalytic activities of these complexes. The complex with the longest linker showed the best catalytic activity for Kumada reactions.Display Omitted
Keywords: N-heterocyclic carbene; Bidentate ligand; Nickel complex; Carbonato ligand;

Solvent-free synthesis of new metal phosphite structures varying from 1D chain to 2D slab and 3D network by Chunmei Duan; Daibing Luo; Qian Wang; Yurong Deng; Zhien Lin (79-82).
Three new metal phosphites, Cd(bpy)(H2PO3)2 (1), (H3O)2  · Co3(HPO3)4 (2), and H2dmen · Zn3(HPO3)4 (3), have been synthesized in a solvent-free flux of phosphorus acid, where bpy = 2,2′-bipyridine, and dmen = N,N-dimethylethylenediamine. Compound 1 represents the first example of cadmium phosphite incorporating an organic ligand. It has a 1D chain-like structure containing corner-sharing 4-rings. Compound 2 has a 2D slab-like structure containing Co3O12 trimers. Compound 3 has a 3D network with corner-sharing 4-ring chains linked by zinc ions. Upon photoexcitation at 286 nm, compound 1 exhibits extensive photoluminescence.Three metal phosphites have been synthesized under solvent-free conditions. These compounds display different structures varying from 1D chain to 2D slab and 3D framework.Display Omitted
Keywords: Solvent-free synthesis; Crystal structure; Open framework; Metal phosphite; Luminescence;

Three hydrogen-bonding frameworks based on N―H⋯N and N―H⋯O Hbond linkages have been synthesized and structurally characterized by using ntb (tris(2-benzimidazoylmethyl)amine) to react with two Cd(II) salts in the presence of dysfunctional bridging spacers of NaN3, 4'4-bipy and H2tpa (terephthalic acid) respectively. The building blocks of three complexes exhibit dumbbell-shape which stacks each other in the lattice leading to three 3D hydrogen-bonding frameworks with diversiform topology net of distorted NaCl net, (4,4) layer and 424  · 64 net.Three hydrogen-bonding frameworks have been synthesized via assembly of dumbbell-shape building units which were tunable by the length of spacers. The inerrant N―H⋯N and N―-H⋯O hydrogen-bonding recognition between ntb and the counter anions is responsible for the assembly of dumbbell-shape coordinated building block.Display Omitted
Keywords: Hydrogen-bonding self-assembly; Dumbbell-shape; Tripodal; Spacers;

A 3D luminescent Zn(II) coordination polymer with rutile-type topology by Jian Wu; Jian-Qiang Liu; Fu-min Wang; Tie Wu; Wang Jun (87-89).
A new coordination network, namely {[Zn(bce)(H2O)]}n (1) (H2bce = 1,2-bis(4-carboxy-phenoxy)ethane), is reported. Complex 1 shows a 3D (3,6)-connected rutile (rtl) topology. The luminescence study indicates that the title compound emits bright green fluorescence and possesses moderate fluorescence lifetimes (τ = 2.26 ns).A new coordination network shows a 3D (3,6)-connected rutile (rtl) topology. In addition, the 3D luminescent behavior and lifetime of the title compound has also been investigated.Display Omitted
Keywords: Luminescence; Structure; Topology; Dicarboxylate;

New neodymium hydroxo-oxalate and oxalate [Nd6(H2O)6(C2O4)7(OH)4]·4H2O (1) and [Nd2(H2O)4(C2O4)3]·2H2O (2) were synthesized by hydrothermal reaction at 150 °C between neodymium nitrate and oxalic acid solutions at pH = 10–11 obtained by adding various monoamines. The structures were determined from single-crystal X-ray diffraction data. The two compounds crystallize in the monoclinic system with space group P21/c and a = 17.4384 (11), b = 8.1717 (5), c = 12.9929 (7), β = 94.66 (1)°, V = 1845.38 (19) Å3, Z  = 2 for 1 and a = 9.8249 (2) Å, b = 8.2487 (2) Å, c = 10.1911 (3) Å, β = 99.09 (1), V = 815.53 (4) Å3, Z = 2 for 2. Full matrix least-squares refinement yielded R1  = 0.0365 and 0.0267 for 6033 and 3382 independent reflections for 1 and 2 respectively. In 2, the three-dimensional neodymium–oxalate arrangement results from dimeric units of edge shared NdO9 polyhedra connected through oxalate ions acting as bis-bidentate. In 1, the neodymium atoms are connected through μ 2-OH and μ 3-OH ions to form a hexanuclear inorganic core [Nd6(OH)4(H2O)6] with an unprecedently reported geometry leading to a hexanuclear polyhedra block. The blocks are connected through an O–O bridge involving two oxygen atoms of two oxalate ions to build a centipede-like ribbon. The ribbons are further connected through oxalate ions to form a three dimensional neodymium oxalate arrangement. In 1, oxalates adopt four distinct bridging modes of coordination, μ 2, μ 3, μ 4 and μ 5.[Nd6(H2O)6(C2O4)7(OH)4]⋅4H2O consists in neodymium atoms connected through μ 2-OH and μ 3-OH ions (in light purple) forming an unprecedentedly reported hexanuclear inorganic core [Nd6(OH)4(H2O)6] connected through an O―O bridge involving two oxygen atoms of two oxalate ions to build a centipede-like Nd skeleton (in blue).Display Omitted► [Nd6(H2O)6(C2O4)7(OH)4].4H2O and [Nd2(H2O)4(C2O4)3].2H2O: structure and synthesis. ► NdO9 condensation up to six polyhedra blocks in [Nd6(H2O)6(C2O4)7(OH)4].4H2O. ► μ5:η1221 bridging mode of an oxalate group in [Nd6(H2O)6(C2O4)7(OH)4].4H2O.
Keywords: Neodymium oxalate; Hydrothermal synthesis; Hexanuclear inorganic block;