Inorganic Chemistry Communications (v.35, #C)

Contents List (iii-xxv).

Retraction notice to Above room-temperature performance of the molecular ferroelectric: bis(imidazolium) L-tartrate by Zhihua Sun; Shuquan Zhang; Chengmin Ji; Shigeng Li; Xiaojun Shi; Junhua Luo (R1).

Two new Cd(II) coordination polymers, namely [Cd3(Hdatrz)2(L1)3(H2O)2] n ·2n(H2O) (1) and [Cd2(Hdatrz)(L2)2] n (2) (HL1 = benzoic acid, H2L2 = iminodiacetic acid, Hdatrz = 3,5-diamino-1,2,4-triazole), have been synthesized by combining the mixed ligands of HL1/H2L2 and Hdatrz with Cd(II) salts under hydrothermal conditions. Single-crystal X-ray diffraction analysis reveals that the structure of 1 features a two-dimensional (2D) layer structure based on Cd(II)-Hdatrz layer and the structure of 2 features a three-dimensional (3D) pillar-layered framework based on Cd(II)-L2 layer and Hdatrz pillars. Moreover, luminescent properties of compounds 12 have been also investigated in the solid-state at room temperature.Presented here are two new Cd(II) coordination polymer, namely [Cd3(Hdatrz)2(L1)3(H2O)2] n ·2n(H2O) (1) and [Cd2(Hdatrz)(L2)2] n (2) (HL1 = benzoic acid, H2L2 = iminodiacetic acid, Hdatrz = 3,5-diamino-1,2,4-triazole). Compound 1 presents a two-dimensional (2D) layer structure, and Compound 2 presents a three-dimensional (3D) pillar-layered framework.Display Omitted
Keywords: Hydrothermal synthesis; 3,5-Diamino-1,2,4-triazole; Pillar-layered framework; Luminescence;

An organic–inorganic hybrid Dy(III)-containing polyoxomolybdate based on functionalized diphosphonate ligands by Lu Yang; Pengtao Ma; Xiaoqing Zhang; Jingyang Niu; Jingping Wang (5-8).
A novel Dy(III)-based organodiphosphonate-functionalized polyoxomolybdate [NH2(CH3)2]3{[Dy(DMF)2(H2O)4]3[Dy(DMF)3{(Mo3O8)(O3PCOCH3PO3)}3]2}∙6DMF·2H2O (1) (DMF = N,N-Dimethylformamide) has been synthesized and characterized by elemental analysis, IR spectrum, thermogravimetric analysis (TG), UV spectroscopy, fluorescence spectroscopy and single-crystal powder X-ray diffraction (PXRD). Compound 1 is composed of two monocapped [Dy(DMF)3{(Mo3O8)(O3PCOCH3PO3)}3]6 − subunits and three [Dy(DMF)2(H2O)4]3 + coordination cations, which contain an internal capsule. The UV spectra indicate that compound 1 is stable in the pH range of 2.76–4.75.A novel Dy(III)-based organodiphosphonate-functionalized polyoxomolybdate [NH2(CH3)2]3{[Dy(DMF)2(H2O)4]3[Dy(DMF)3((Mo3O8)(O3PCOCH3PO3))3]2}∙6DMF·2H2O has been successfully synthesized. The polyanion displays a cage-like structure, which is constructed from two monocapped [Dy(DMF)3((Mo3O8)(O3PCOCH3PO3))3]6 − fragments and three [Dy(DMF)2(H2O)4]3 + subunits.Display Omitted
Keywords: Polyoxomolybdate; Organophosphonates; Dy(III)-containing; Aqueous solution stability;

Reaction of hydrogen peroxide with ethylenediaminetetraacetato lanthanides results in the formation of water-soluble isomorphous N-oxido ethylenediaminetetraacetato lanthanides K5[Ln(edtaO2)2] · 12H2O [Ln = La (1), Ce (2), Nd (3), H4edta = ethylenediaminetetraacetic acid C10H16O8N2] in weak basic solution, where lanthanide ions are octa-coordinated by two quardentate N-oxido edta ligands, resulting in a distorted anti-tetragonal prism. Based on the comparisons of solid and solution 13C NMR spectra, these compounds are fully dissociated in solution. Catalytic reaction of K5[La(edtaO2)2]·12H2O shows 96% conversion for the reaction of pyridine to pyridine N-oxide at 70 °C.Lanthanum N-oxido ethylenediaminetetraacetate catalyzes the oxidation of pyridine with hydrogen peroxide with a yield of 96%. Peroxo groups are trapped by ethylenediaminetetraacetate.Display Omitted
Keywords: Lanthanide; Ethylenediaminetetraacetate; N-oxide; Hydrogen peroxide; Catalysis;

Uranyl complex with phenolate–sulphonate and diphenyldiazenecarbohydrazonate ligands by Reza Solhnejad; Fidan N. Bahmanova; Abel M. Maharramov; Rafiga A. Aliyeva; Famil M. Chyragov; Atash V. Gurbanov; Gunay S. Mahmudova; Kamran T. Mahmudov; Maximilian N. Kopylovich (13-15).
Reaction of uranyl nitrate hexahydrate with 3-(2-(2,4-dioxopentan-3-ylidene)hydrazinyl)-2-hydroxybenzenesulfonic acid (H3L) and bis((E)-phenyldiazenyl)methanone (bpm) yields mononuclear zwitterionic uranyl complex, [UO2(HL)(bpm)(H2O)2]∙3H2O (1), which was characterized by IR, ESI-MS spectroscopies, and elemental and X-ray single-crystal analyses. In 1, the uranium center is in distorted pentagonal bipyramidal geometry with HL2 − and bpm ligands coordinated in equatorial plane. The coordination to uranyl and intramolecular hydrogen bonding assist the tautomerization of bpm and formation of zwitterion.New uranyl complex with phenolate–sulphonate and diphenyldiazenecarbohydrazonate ligands are synthesized and fully characterized.Display Omitted
Keywords: Uranyl complexes; Hydroxybenzenesulfonic acid; Bis(phenyldiazenyl)methanone; Complex zwitterion;

Cytotoxic, cell apoptosis and DNA binding properties of some ternary Cu(II) complexes with a reduced Schiff base ligand and heterocyclic bases by Lei Jia; Hong-xin Cai; Jun Xu; Heng Zhou; Wei-na Wu; Fei-fei Li; Yuan Wang; Xiao-wei Pei; Qin Wang (16-18).
Three mononuclear mixed ligand Cu(II) complexes of the type [Cu(L)(DTHA)]H2O⋅CH3OH, where H2DTHA is 2-(3,5-di-tert-butyl-2-hydroxybenzylamino) acetic acid and the co-ligand L is 1,10-phenanthroline (phen, 1), dipyrido[3,2-d:2′,3′-f]quinoxaline (dpq, 2) dipyrido [3,2-a:2′,3′-c]phenazine (dppz, 3) have been isolated and characterized. Absorption and emission spectral studies and viscosity measurements indicated that 3 interacts with DNA more strongly than all of the other complexes through intercalation mode. Furthermore, cytotoxicity studies on the tested four cell line indicated that they can efficiently inhibit the cell proliferation in a time-dependent manner, and the Hoechst 33258 staining assays have also been employed in finding the extent of DNA damage.Three new ternary copper(II) complexes 13 are synthesized and characterized. All of them show significant cytotoxic, cell apoptosis and DNA-biding activities.Display Omitted
Keywords: Cell apoptosis; Cytotoxicity; DNA binding properties; Reduce Schiff base; Hoechst 33258; Ternary Cu(II) complexes;

A rare one-dimensional Dy(III) complex exhibiting slow magnetic relaxation by Bo Na; Yu-Xia Wang; Tian Han; Wei Shi; Peng Cheng (19-21).
A rare 1D lanthanide complex {[Dy(HPA)2(NO3)2]NO3}n (1) (HPA = (4-pyridylthio)acetic acid) was synthesized and structurally characterized. Under the given dc field, both in-phase and out-of-phase frequency dependence signals are observed in alternating current (ac) magnetic measurements, revealing the slow magnetic relaxation of 1.A new Dy(III) complex was synthesized and structurally characterized by X-ray single-crystal diffraction. Magnetic measurements indicate the prevalence of quantum tunneling effect at low temperature.Display Omitted
Keywords: Dysprosium; Crystal structure; Magnetic property; Frequency dependence;

We report preparation and characterization of a novel complex cis–mer [Co(L)2]I2 CH3OH (1) (L-N,N-bis(1-(3,5-dimethylpyrazolylmethyl)amine)) isolated from the [Co0–1-hydroxymethyl-3,5-dimethylpyrazole–MoO3–NH4I] system. A two-ring scorpionate ligand (L) was obtained in situ via redox and condensation processes. The catalytical properties of MoO3 are responsible for the formation of this atypical scorpionate ligand. Compound (1) crystallizes in the orthorhombic space group Pna21 with a  = 24.5578(14) Å, b  = 13.8388(8) Å, c  = 9.6072(7) Å, V  = 3265.0(4) Å3 and Z  = 4. The metal ion coordinates through six nitrogen atoms which belong to two tridentate ligands forming a deformed octahedron. The complex was characterized by IR, FIR, UV–VIS and magnetic investigations. The ligand was ranked in the spectrochemical series between imidazole and bipyridine. The crystal field splitting of tridentate N-donor L was found to be smaller in comparison to e.g. bidentate bipyridine.The novel complex cis–mer [Co(L)2]I2 CH3OH (L-N,N-bis(1-(3,5-dimethylpyrazolylmethyl)amine)) was isolated from the [Co0–MoO3-1-hydroxymethyl-3,5-dimethylpyrazole–NH4I] system. A two-ring scorpionate ligand (L) was obtained in situ.Display Omitted
Keywords: Cobalt; Crystal structure; N,N-bis(1-(3,5-dimethylpyrazolylmethyl)amine); Scorpionates; X-ray data;

The new tetrathiafulvalene-functionalized bispyrazole ligand (L) and the corresponding tricarbonyl rhenium(I) complex (4) have been synthesized and structurally characterized. Their absorption spectra and redox behaviors have been recorded, and the absorption spectral changes of L upon addition of NOPF6 have also been studied in detail.The tricarbonyl (chloro) rhenium(I) complex with the new electroactive tetrathiafulvalene-based bispyrazole ligand with the amide bridge, N-(2,2-di(1H-pyrazol-1-yl)ethyl)-4′,5′-bis(methylthio)-[2,2′-bi(1,3-dithiolylidene)]-4-carboxamide (L), have been prepared and structurally characterized. The absorption and electrochemical properties of these new compounds have been studied.Display Omitted
Keywords: Syntheses; Crystal structures; Tetrathiafulvalene; Pyrazole ligands; Rhenium complexes;

Assembly of CuBr and 1,6-bi(benzotriazole)hexane under solvothermal conditions modulated by alkali metal cations by Quan-Guo Zhai; Yong-Ni Zhao; Shu-Ni Li; Yu-Cheng Jiang; Man-Cheng Hu (31-33).
The addition of alkali metal bromide effectively controlled the assembly processes of flexible 1,6-Bi(benzotriazole)hexane (BBTH) ligand and CuBr under solvothermal conditions, and led to four different crystalline solids, namely, {K[Cu6Br7](BBTH)} n (1), {[CuBr]4(BBTH)} n (2), {[CuBr]2(BBTH)} n (3), and Cs3Cu2Br5 (4). The cuprous bromide inorganic skeletons vary from [Cu4Br4] double chain (in 2), [Cu6Br7] zigzag ribbon (in 1), [Cu2Br2] single helix (in 3) to binuclear [Cu2Br5] cluster (in 4) with the alkali metal cations changing from Na+, K+, Rb+ to Cs+. Cisoid-BBTH ligands in 1 and 2 link adjacent inorganic chains to form 2D organic–inorganic hybrid layers, but transoid-BBTH in 3 connects cuprous bromide chain to give a 3D rod-packing framework.Alkali metal bromide effectively modulated the assembly of flexible 1,6-Bi(benzotriazole)hexane (BBTH) ligand and CuBr under solvothermal conditions.Display Omitted
Keywords: 1,6-Bi(benzotriazole)hexane; CuBr; Alkali metal; Organic–inorganic hybrid solid;

Two new 2p–3d–4f heterometallic coordination polymers based on 3,5-pyrazoledicarboxylic acid: synthesis, crystal structures and magnetic properties by Yan Wang; Xing-Xing Li; Huan Jiang; Bo-Wen Xia; Ning Deng; Yan-Wu Zhu; Guan-Ping Jin; Xiao-Min Ni; Jian-Bo He (34-37).
Two new 2p–3d–4f heterometallic coordination polymers, [NaCuGd(pdc)2(H2O)7  ∙ 2H2O]n (1) and [NaCuEu(pdc)2(H2O)7  ∙ 2H2O]n (2), have been synthesized based on 3,5-pyrazoledicarboxylic acid (H3pdc). Single-crystal X-ray diffraction analysis reveals that complexes 12 are isostructural and both of them display an infinite two-dimensional brickwall-like layer structure consisting of three metal ions and bridged pyrazoledicarboxylate ligands. Magnetic properties of the complexes have been investigated in detail. Furthermore, free-ion approximation was used to fit the magnetic data and a good theory-experiment agreement was obtained for both 1 and 2.Complexes 12 are isostructural and they both display 2D brickwall-like layer structure with the pyrazoledicarboxylate bridged ligand in two different coordinated modes.Display Omitted
Keywords: Pyrazoledicarboxylate; 3d–4f; Coordination polymer; Magnetism;

Two new supramolecular compounds, [Cd(H2PIDC)2(H2O)]·H2O (1) and {[Cd(H2PIDC)2(H2O)]·2H2O}n (2) (H3PIDC = 2-(pyridine-2-yl)-1H-imidazole-4,5-dicarboxylic acid), have been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. Compound 1 contains discrete mononuclear structure, and compound 2 consists of one-dimensional left- and right-helix chains. Both are constructed into high-dimensional supramolecular frameworks by strong non-covalent hydrogen bonding and ππ stacking interactions. In addition, they were characterized by IR and elemental analysis, and their fluorescence properties in the solid state at room temperature have also been investigated.Two new cadmium coordination compounds were synthesized through hydrothermal reaction between cadmium salt and H3PIDC. 1 contains discrete mononuclear structure, and 2 consists of one-dimensional left- and right-helix chains. Their fluorescence properties in the solid state at room temperature have also been investigated.Display Omitted
Keywords: Hydrothermal synthesis; Helical chain; Hydrogen bonding; ππ stacking; Luminescence property;

A novel helical cadmium(II) coordination polymer cis,cis,trans-{[Cd(HIDC)(H2O)2]·1/3H2O}n (1) has been obtained by the solvothermal reaction of hydrated CdCl2 with 2H-imidazole-4,5-dicarbonitrile (HIMDN) in the presence of NH3·H2O. The packing of the six neighboring polymeric helical chains of the complex leads to a 1-D channel, which is occupied by lattice water molecules. The solid-state luminescence properties of 1 have been investigated at room temperature.A novel helical cadmium(II) coordination polymer cis,cis,trans-{[Cd(HIDC)(H2O)2]·1/3H2O}n (1) has been obtained by the hydrothermal reaction of hydrated CdCl2 with 2H-imidazole-4,5-dicarbonitrile. The packing of the six neighboring polymeric helical chains of the complex leads to a 1-D channel. The solid-state luminescence properties of 1 have been investigated at room temperature.Display Omitted
Keywords: Helix; Porous structure; In-situ ligand reaction; Luminescence;

Two one-dimensional (1D) germanium(IV) coordination polymers (CPs) containing macrocyclic tetraaza[14]annulene, [Ge(tmtaa)(L)] n [tmtaa = tetraaza[14]annulene, L = 1,4-benezedicarboxylate 1; 2,5-dihydroxyl-1,4-benezedicarboxylate, 2], are synthesized and characterized. The temperature dependence of the electrical conductivity (σ) for 1 or 2 indicates region of rising dσ/dT (the conductivity increases with increasing temperature), suggesting semiconductor-like charge transport in the stacking direction. The room temperature electrical conductivities for 1 and 2 are 1.52 × 10− 8  S cm− 1 and 1.18 × 10− 5  S cm− 1, respectively, which are obviously higher than those of most 1D metallophthalocyanine- and metalloporphyrine-containing CPs. Though the crystal structures of 1 and 2 are similar, 2 exhibits better electrical conductivity which is about three orders higher than that of 1. This may be due to the protonic conduction existing in 2. Furthermore, 1 and 2 show outstanding thermal stability. These results suggest the potential applications of 1 and 2 as semiconductive materials.Two 1D Ge(IV) coordination polymers containing macrocyclic tetraaza[14]annulene, 1 and 2, show notable semiconducting property. Though the structures of 1 and 2 are similar, 2 exhibits better electrical conductivity which is about three orders higher than that of 1. This may be due to the protonic conduction existing in 2.Display Omitted
Keywords: Germanium(IV); Tetraaza[14]annulene; Coordination polymer; Crystal structure; Semiconductor; Protonic conduction;

X-ray structure and magnetic properties of a novel dinuclear heterobimetallic CoIII–CN–FeIII compound of the composition [{Co(3EtO-L5)}(μ-CN){Fe(L4)(Cl)}] (2) is reported. Adjacent complex molecules are connected through intermolecular N―H⋅⋅⋅Cl hydrogen bonds into 1D supramolecular chains. Such a compound can be considered as a potential building block for the preparation of Prussian blue analogues of high nuclearity showing interesting magnetic properties.X-ray structure and magnetic properties of a dinuclear heterobimetallic CoIII–CN–FeIII compound of the composition [{Co(3EtO-L5)}(μ-CN){Fe(L4)(Cl)}] (2) is reported.Display Omitted
Keywords: Heterobimetallic; Structure; Magnetism; Cyanidometallates;

We report ultra-sonication assisted morphological evolution in hexagonal macrocrystals of {V10O28} type polyoxometalate system [C5H11N]6[V10O28]·[CH3COOH]4·2H2O (1) as a function of sonication temperatures. Field emission scanning electron microscopy (FESEM) as well as transmission electron microscopy (TEM) studies reveal that at room temperature, sonication of macrocrystals results in the formation of spherical nanoparticles, that are transformed to nano-rods at the sonication temperature of 50 °C. The morphology is transformed from nano-rods to micro-flowers through hexagonal shaped microcrystals as the sonication temperature rose from 50 to 80 °C. It is observed that the hexagonal morphology of the original crystal is retained after a complete cycle (from 80 °C to complete evaporation of solvent) of morphological transitions. Compound 1 is unambiguously characterized by single crystal X-ray structure determination.Single crystals of compound [C5H11N]6[V10O28]·4CH3COOH·2H2O (1) have been isolated by slow diffusion of piperidine into the sodium meta-vanadate solution, acidified with acetic acid. Compound 1 undergoes reversible morphological transitions between nano-rods and micro-sized hexagonal structures as a function of sonication temperatures.Display Omitted
Keywords: Polyoxometalates; Nanoparticles; Electron microscopy; Morphological transitions; Ultra-sonication; Supramolecular interactions;

A new heptanuclear complex [{Cu(TPA)CN}6Mo(CN)2][ClO4]8 (1) (TPA = tris(2-pyridylmethyl)amine) was formed by the reaction of [Cu(TPA)]2 + cations and K4Mo(CN)8. The octacyanomolybdate core is encapsulated by six mononuclear copper cations via cyano bridges. 1 Crystallizes in monoclinic space group P21/n with a  = 22.30(2) Å, b  = 27.13(3) Å, c  = 24.35(2) Å, β  = 94.10(2)°, and Z  = 4. Variable temperature magnetic measurements have demonstrated that very weak antimagnetic interaction between the nearest paramagnetic CuII centers at low temperature is exhibited, transferred by ―NC―Mo―CN― bridging units.A new heptanuclear complex was formed by the utilization of K4Mo(CN)8. The octacyanomolybdate core is encapsulated by six mononuclear copper cations via cyano bridges. Variable temperature magnetic measurements have demonstrated that very weak antimagnetic interaction between the nearest paramagnetic CuII centers at low temperature is exhibited.Display Omitted
Keywords: Heptanuclear compound; Cyanide; Antimagnetic interaction; Octacyanomolybdate;

A rare pentanuclear CuII-based coordination framework exhibiting coexistence of antiferromagnetic and ferromagnetic couplings by Jun Zhao; Dong-Sheng Li; Ya-Pan Wu; Jing-Jing Yang; Wen-Wen Dong; Kun Zou (61-64).
A unique pentacopper(II) cluster-based 3-D coordination framework, [Cu5(nip)4(μ 3-OH)2-(dps)2(H2O)4] n , has been prepared by hydrothermal reaction of Cu(II) with 5-nitroisophthalic acid (H2nip) and 4,4′-dipyridylsulfide ligands (dps), which exhibits a 6-connected pcu net and coexistence of antiferromagnetic and ferromagnetic couplings.A novel Cu(II)-coordination framework which represents the first pentacopper-based pcu network, and demonstrates both ferro- and antiferromagnetic intramolecular interactions in the pentanuclear copper(II) clusters.Display Omitted
Keywords: Pentacopper(II) cluster; Hydrothermal reaction; pcu net; Antiferromagnetic and ferromagnetic couplings;

The mixed-valence coordination polymer, [Cu(S2CNPr2)2]2[ClO4], containing both square-planar Cu(II) and Cu(III) centres, has been prepared and crystallographically characterised. In the solid-state it consists of a chain of alternating Cu(II) and Cu(III) centres held together by intermolecular Cu–S interactions, while the perchlorate anions are not metal coordinated. For comparison the crystal structure of [Cu(S2CNPr2)2]2 has been re-determined at 150 K.The mixed-valence coordination polymer, [Cu(S2CNPr2)2]2[ClO4], has been prepared and crystallographic studies show that it consists of alternating square-planar paramagnetic copper(II) and diamagnetic copper(III) centres, the chain being held together by intermolecular copper–sulphur interactions, while the perchlorate anions are non-coordinating.Display Omitted
Keywords: Mixed-valence; Coordination polymer; Dithiocarbamate; Copper(III); Copper(II);

A fluorescent sensor with mixed N/O/Se donor atoms for probing Zn(II) ion by Fei Xiao; Jin Shen; Jian Qu; Su Jing; Dun-Ru Zhu (69-71).
1-(Ferrocenylseleno)-3-(8-hydroxyquinoline)-propane was synthesized and studied as a fluorescent sensor for Zn2 + ion. It demonstrates good selectivity for sensing Zn2 + via ICT mechanism.1-(Ferrocenylseleno)-3-(8-hydroxyquinoline)-propane was synthesized and its structure was determined. As a fluorescent sensor, it demonstrates good selectivity for sensing Zn2 + via ICT mechanism.Display Omitted
Keywords: Fluorescent sensor; Ferrocene; 8-Quinoline; Mixed donor atoms;

Magnetostructural study of tetracoordinate cobalt(II) complexes by Ján Titiš; Jozef Miklovič; Roman Boča (72-75).
Five tetracoordinate cobalt(II) complexes of the formula [CoX2L2] have been investigated by SQUID magnetometry; X is the (pseudo)halide ligand and L is the N- or P-donor ligand. The complexes exhibit a moderate magnetic anisotropy expressed by the zero-field splitting parameter D. Its value ranges as D/hc  = −13 to + 5 cm 21 −1. The value of the D-parameter increases with the angular deformation δ that measures a deviation of the X–Co–X and L–Co–L angles with respect to the ideal tetrahedron.Zero-field splitting parameter D was determined by analyzing the SQUID-magnetometric data for five tetracoordinate cobalt(II) complexes of the formula [CoX2L2]. It ranges as D/hc  = − 13 to + 5 cm−1 and correlates with the angular deformation parameter d that measures a deviation with respect to the ideal tetrahedron.Display Omitted
Keywords: Cobalt(II) complex; Crystal structure; Zero-field splitting; Magnetostructural correlation;

Reaction of the 2-D MOF [AgL] n ·nH2O (1; L = 4-cyanobenzoate) with pyrazine (L′) in water yielded [Ag2L2L′] n ·2nH2O (2) with a chain-like structure. Compound 1 features tunable yellow-to-white photoluminescence when its wavelength of excitation light varies. The photoluminescence of 2 obviously differs from that of 1: the former displays intense yellowish green phosphorescence with a shorter lifetime of ~ 3.58 μs and an unresolved peak shape, and does not exhibit tunable photoluminescence upon irradiation of 280–380 nm UV light. Electron transition from the [Ag2(COO)2] cluster to pyrazine is probably responsible for the phosphorescence of 2 based on the experimental and theoretical results.Reaction of the 2-D MOF [Ag(4-cyanobenzoate)] n ·nH2O (1) with pyrazine in water yielded [Ag2(4-cyanobenzoate)2(pyrazine)] n ·2nH2O (2) with a chain-like structure. Compound 1 features tunable yellow-to-white photoluminescence, while compound 2 only displays yellowish green phosphorescence. The luminescence mechanism of 1 clearly differs from that of 2.Display Omitted
Keywords: Ag(I); Argentophilic interaction; Carboxylate; Phosphorescence; Tunable photoluminescence;

New dinuclear complexes with the bridging S―S coupled and dimerized quinoxaline-2,3-dithiolate (dsqdt) ligand, [TpPh2M(dsqdt)MTpPh2] (TpPh2  = hydro-tris(3,5-diphenylpyrazol-1-yl)borate; M = Co, 1; M = Ni, 2; M = Mn, 3), were prepared. X-ray crystal structure studies for complexes 13 indicate that the dsqdt ligand forms the unique κ2-coordinated mode through S and N atoms from the same qdt unit. The absorption spectra, redox behavior and magnetic properties of the compounds are reported.Three dinuclear complexes with the bridging S―S coupled and dimerized quinoxaline-2,3-dithiolate ligand (dsqdt) have been synthesized and structurally characterized. The dsqdt ligand shows the new κ2(S, N)-coordination mode. The absorption spectra, electrochemical and magnetic properties for all complexes are studied.Display Omitted
Keywords: Dinuclear complexes; Quinoxaline-2,3-dithiolate; Coordination mode; Crystal structures; Syntheses;

This paper reports two 1-D chain-like compounds, namely, Co(mb)2(bimb)0.5 (1) and Ni(mb)2(bimb)0.5 (2) (mb = 4-methylbenzoate and bimb = 1,4-bis(imidazol-1-yl)-butane), which have been obtained via hydrothermal reaction and characterized by single-crystal X-ray diffraction, IR and elemental analysis. The formations of 12 are based on the linkage between the paddle-wheel shaped secondary building block units (SBUs) through long-chain bimb ligands. Compound 1 exhibits ferrimagnetic-like behavior, while compound 2 undergoes an unusual field-induced metamagnetic phase transition.This paper reports two 1-D chain-like compounds which are based on the linkage between the paddle-wheel shaped secondary building block units (SBUs) through long-chain bimb ligands. Compound 1 exhibits ferrimagnetic-like behavior, while compound 2 undergoes an unusual field-induced metamagnetic phase transition.Display Omitted
Keywords: Flexible bis(imidazole) ligands; Ferromagnetism; Metamagnetism;

A defect dicubane-like complex, [Ni4{(2-py)2C(OH)O}2{(2-py)2C(OCH3)O}2 (N3)4]·2CH3CN·2H2O (1) and a cubane-like complex, [Ni4{(2-py)2C(OH)O}3(hmp)3(NO3)].(NO3)·3H2O (2) (Hhmp = 2-hydroxymethylpyridine), were prepared by reacting NiCl2·6H2O with (py)2CO, NaN3 and NMe4OH in MeOH/MeCN and the similar reaction exception the N3 anion replaced by multidentate chelating ligand Hhmp, respectively. X-ray analysis revealed that four Ni2 + ions, four O atoms and two N atoms in 1 were located at the vertices of a defect dicubane; by contrast, four Ni2 + ions and four O atoms in 2 occupied alternate vertices of a [Ni4O4] cubane. Magnetic studies indicated the presence of overall ferromagnetic interactions between Ni2 + ions within both complexes.Two complexes [Ni4{(2-py)2C(OH)O}2{(2-py)2C(OCH3)O}2 (N3)4]·2CH3CN·2H2O (1) and [Ni4{(2-py)2C(OH)O}3(hmp)3(NO3)]·(NO3)·3H2O (2) have been prepared and characterized. While four Ni2 + ions, four O atoms and two N atoms in 1 are located at vertices of a defect dicubane, four Ni2 + ions and four O atoms in 2 occupy alternate vertices of a [Ni4O4].Display Omitted
Keywords: Tetranuclear Ni complex; Mixed-chelating ligand; Multidentate chelating ligand; Crystal structure; Magnetic property;

A new octanuclear Fe8 cluster with antiferromagnetic coupling by Gang Xiong; Yin-Ling Hou; Jian-Zhong Cui; Bin Zhao (89-91).
A new cluster [Fe84-O)3(teaH)3(tea)(IBA)6(H2O)3](NO3)3·3H2O (1) (teaH3  = triethylolamine, IBA = isobutyric acid) was synthesized and structurally characterized. The octanuclear cluster is constructed by three Fe4 tetrahedrons via sharing the edges. Magnetic susceptibility measurement indicates that the antiferromagnetic couplings exist between adjacent FeIII centers with zero spin ground state. Cyclic voltammogram exhibit an irreversible redox process.A new cluster [Fe84-O)3(teaH)3(tea)(IBA)6(H2O)3](NO3)3·3H2O (1) (teaH3  = triethylolamine, IBA = isobutyric acid) was synthesized and structurally characterized. Magnetic susceptibility indicates that the strong antiferromagnetic couplings exist between adjacent FeIII centers with zero spin ground state.Display Omitted
Keywords: Iron cluster; Magnetic property; Antiferromagnetic coupling; Cyclic voltammogram;

Cyclopentasilane Si5H10 (CPS) – a liquid silicon precursor – was crystallized in situ at − 100 °C which allowed determination of the single crystal X-ray structure, showing short intermolecular distances below the sum of the v.d.Waals radii of the corresponding atoms. Further characterization included a thermal analysis with mass spectrometry (TG/MS) of the segregated species hydrogen, mono- and disilane.Cyclopentasilane Si5H10 (CPS) – a liquid precursor for low temperature deposition of silicon films – was crystallized in situ at − 100 °C which allowed the determination of the first single crystal X-ray structure of an oligosilane. Further characterization included a thermal analysis with a mass spectroscopic analysis of the segregated fragments.Display Omitted
Keywords: Silicon; Silanes; Precursors; Molecular structure; Thermal transformation;

A new luminescent platinum(II) chloride complex of 6-(5-trifluoromethyl-1,2,4-triazol-3-yl)-4,4′-dimethyl-2,2′-bipyridine by Jing-Lin Chen; Xiu-Xiu Chen; Xiu-Zhen Tan; Jin-Yun Wang; Xing-Feng Fu; Li-Hua He; Yang Li; Gui-Quan Zhong; He-Rui Wen (96-99).
A new Pt(II) chloride complex Pt(ftmbpy)Cl (1) with deprotonated 6-(5-trifluoromethyl-1,2,4-triazol-3-yl)-4,4′-dimethyl-2,2′-bipyridine terdentate ligand has been synthesized and characterized. Complex 1 gives a distorted square-planar configuration with a mono-anionic chelate ftmbpy, and displays a 1-D zigzag head-to-tail arrangement along the b axis formed via intermolecular π⋯π stacking and Pt⋯Pt interactions. A relatively weak broad absorption is observed at 360–435 nm in dilute CH2Cl2 solution at room temperature, tentatively ascribed to metal-to-ligand charge transfer (1MLCT) excited state with some mixing of intra-ligand 1ππ* character inside ftmbpy, as supported by TD-DFT analysis. It is demonstrated that complex 1 is emissive in both solution and solid states and exhibits the concentration-dependent luminescence properties originating from intermolecular Pt⋯Pt and π⋯π interactions, and the introduction of substituents (e.g. two methyl groups) into the 2,2′-bipyridyl ring is effective for improving the solubility of Pt(II) complexes.A new emissive Pt(II) chloride complex Pt(ftmbpy)Cl (1) with deprotonated 6-(5-trifluoromethyl-1,2,4-triazol-3-yl)-4,4′-dimethyl-2,2′-bipyridine chelate has been synthesized and characterized. Complex 1 displays a 1-D zigzag head-to-tail packing array along the b axis and the concentration-dependent luminescence properties as a result of intermolecular Pt···Pt and π···π interactions.Display Omitted
Keywords: Platinum(II); Crystal structure; Photoluminescence; 2,2′-Bipyridyl 1,2,4-triazole;

A new ruthenium biimidazole-like anion receptor featuring two “chelating” N―H⋯O intramolecular hydrogen bonds, [Ru(bpy)2(DNBbimH2)](PF6)2 (2·(PF6)2) (bpy = 2,2′-bipyridine; DNBbimH2  = 5,5′,6,6′-tetramethyl-7,7′-dinitro-2,2′-bibenzimidazole), has been synthesized. Its anion-binding ability towards different anions in acetonitrile has been studied.A new ruthenium biimidazole-like anion receptor featuring two “chelating” N―H⋯O intramolecular hydrogen bonds, [Ru(bpy)2(DNBbimH2)](PF6)2 (bpy = 2,2′-bipyridine; DNBbimH2  = 5,5′,6,6′-tetramethyl-7,7′-dinitro-2,2′-bibenzimidazole), has been synthesized. It shows strong affinity towards Cl and Br, binds weakly to I, and shuts out NO3 and HSO4 .Display Omitted
Keywords: Anion receptor; Biimidazole; Intramolecular hydrogen bond; Ruthenium;

Spectral, XRD, SEM and biological properties of new mononuclear Schiff base transition metal complexes by M.I. Khan; Ayub Khan; Iqbal Hussain; Murad Ali Khan; Saima Gul; Mohammad Iqbal; Inayat-Ur-Rahman; Fazli Khuda (104-109).
Six new transition metal complexes derived from the reaction of 4(4-(dimethylamino) benzylideneamino) benzoic acid and Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) cations, were prepared, isolated and characterized by a range of spectral and analytical methods including UV/Vis, FT IR, NMR, MS, powder XRD, TGA and SEM. The complexes were formed with the deprotonation of the ligand and presented typical six-coordinated octahedral geometry. In addition, the biological activity was evaluated by conducting in vitro anti-bacterial, anti-fungal and anti-leishmanial screenings. All the complexes were found more active than the ligand, while complex 7 revealed biological significance.Six new mononuclear transition metal complexes were synthesized with Schiff base ligand i.e. 4(4-(dimethylamino) benzylideneamino) benzoic acid in 1:2 molar stoichiometry. Analytical data obtained proved the deprotonation of the ligand in distorted octahedral geometry. Zn(II) complex proved an interesting biological significance during the in vitro anti-bacterial and anti-fungal screenings.Display Omitted
Keywords: Schiff base; Transition metal complexes; Anti-bacterial; Anti-fungal; Anti-leishmanial;

Luminescent palladium(0) complexes bearing N-heterocyclic carbene and phosphine ligands by Taro Tsubomura; Hironori Murota; Koichiro Takao (110-112).
Palladium(0) complexes bearing a monodentate phosphine ligand and an N-heterocyclic carbene ligand have been prepared. In these complexes, photophysical properties of the complexes, [Pd(IPr)(PPh3)] and [Pd(IPr)(P(o-tol)3)] have been studied (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene). The emissive excited states have been tentatively assigned to 3MLCT. In addition to the results of the luminescent complexes, the synthesis of the related complexes, [Pd(O2)(IPr)(P(m-tol)3)] and [PdCl(CH2Cl)(IPr)(P(MeOPh)3)] (P(MeOPh)3 =  tris(pmethoxyphenyl)phosphine) have been studied and the structures were characterized by X-ray.The synthesis and luminescent properties of some palladium(0) complexes bearing a monodentate phosphine ligand and an N-heterocyclic carbene ligand have been studied. The synthesis and characterization of structurally related palladium(II) complexes have been also explored in the study.Display Omitted
Keywords: Palladium; Luminescence; N-heterocyclic carbene; Phosphines;

An inorganic–organic hybrid material {[Dy2(SO4)(Himdc)2(H2O)5]·H2O}n featuring organic carboxylic acid and inorganic sulfate and luminescent property by Reshalaiti·Hailili; Li-Xian Chang; Li Wang; Yi-Neng Huang; Wei Qian; Ming-Hua Zeng; Zulipiya·Abulizi (113-116).
Hydrothermal treatment of a mixture of H3imdc (4,5-imidazoledicarboxylic acid), Na2SO4, Dy(NO3)3·6H2O and NaOH generated a novel inorganic–organic hybrid framework, {[Dy2(SO4)(Himdc)2(H2O)5]·H2O}n (1). Its crystal structure contains alternately arranged 1D left- and right-handed helical {Dy(Himdc)}n chains, each helical chain is composed of alternately arranged Dy(1) and Dy(2) ions connected by Himdc2– with bis(bidentate) linking mode. Every three helical chains are bridged by inorganic SO4 2 − anions, which link Dy3 + ions in a tris(monodentate) mode to form a 3D framework. Compound 1 displays intense yellow photoluminescence corresponding to the characteristic 4F9/26HJ transitions of the Dy3 + ion.Hydrothermal treatment of a mixture of H3imdc (4,5-imidazoledicarboxylic acid), Na2SO4, Dy(NO3)3·6H2O and NaOH generated a novel inorganic–organic hybrid framework, [[Dy2(SO4)(Himdc)2(H2O)5·H2O] n (1). Its crystal structure contains alternately arranged 1D left- and right-handed helical {Dy(Himdc)}n chains, each helical chain is composed of alternately arranged Dy(1) and Dy(2) ions connected by Himdc2– with bis(bidentate) linking mode. Every three helical chains are bridged by inorganic SO4 2 − anions, which link Dy3 + ions in a tris(monodentate) mode to form a 3D framework. Compound 1 displays intense yellow photoluminescence corresponding to the characteristic 4F9/26HJ transitions of the Dy3 + ion.Display Omitted
Keywords: Inorganic–organic hybrid; Hydrothermal synthesis; Coordination polymer; Luminescence;

2-Benzoylpyridine N(4)-cyclohexylthiosemicarbazone (HL) and its binuclear copper(II) complex [Cu2(L)2(CH3COO)](ClO4) (1) have been synthesized and structurally characterized. Biological studies, carried out in vitro against human leukemia K562 cells have indicated that 1 indicates significant cytotoxicity with IC50  = 0.37 ± 0.028 μM comparable to cisplatin. Complex 1 promotes a dose-dependent apoptosis in HepG2 cells and the apoptosis is associated with an increase in intracellular reactive oxygen species (ROS) production and reduction of mitochondrial membrane potential (MMP).2-Benzoylpyridine N(4)-cyclohexylthiosemicarbazone (HL) and its binuclear copper(II) complex [Cu2(L)2(CH3COO)](ClO4) (1) were synthesized and characterized. 1 indicates significant cytotoxicity with IC50 = 0.37 ± 0.028 μM against human leukemia K562 cells and promotes a dose-dependent apoptosis in HepG2 cells. Its possible apoptotic mechanism has been evaluated.Display Omitted
Keywords: Thiosemicarbazone; Crystal structure; Cytotoxicity; Apoptosis;

A new polyanion with Dawson-like constitution: [H2SeW18O60]6 − by Lijuan Wang; Wenjuan Li; Lizhou Wu; Xinbo Dong; Huaiming Hu; Ganglin Xue (122-125).
A new tungstoselenite, [H2SeW18O60]6 −, was isolated under acidic medium conditions (pH = 1.7)with the monoprotonated ethylamine as cation. It represents the first example of Se-containing polyoxometalate with unusual Dawson-like construction and has fully been characterized both in solid state and in solution. The high-resolution ESI-MS confirmed that the polyanion at least contains two protons and its proton number can be up to six in solution.The polyanion represents the first example of Se-containing POM with unusual Dawson-like construction. The high-resolution ESI-MS confirmed that the polyanion at least contains two protons and its proton number can be up to six in solution.Display Omitted
Keywords: Polyoxometalates; ESI-MS; Dawson polyanion;

Organometallic benzimidazoles: Synthesis, characterization and antimalarial activity by Patricia Toro; A. Hugo Klahn; Bruno Pradines; Fernando Lahoz; Aurélie Pascual; Christophe Biot; Rodrigo Arancibia (126-129).
A series of ferrocenyl and cyrhetrenyl benzimidazoles were synthesized and characterized. The condensation–cyclization reaction of cyrhetrenecarbaldehyde with 1,2-phenylendiamine or 4-nitro-1,2-phenylendiamine produces only the 2-cyrhetrenyl-benzimidazoles [1-Re-(H, NO2)] whereas with the same diamines, ferrocenecarbaldehyde yields two products: 2-ferrocenyl-benzimidazole [1-Fe-(H, NO2)] and N-ferrocenylmethyl-2-ferrocenyl-benzimidazole [2-Fe-(H, NO2)]. The structures of all products were confirmed by 1H, 13C NMR spectra and MS. The molecular structure of 2-Fe-NO2 was determined by single crystal X-ray analysis. The antimalarial evaluation studies against the CQ susceptible-strain (3D7) and the CQ resistant-strain (W2) of Plasmodium falciparum revealed cyrhetrene conjugates to be most potent of the tested compounds. The presence of the nitro group at the 5-position of organometallic-benzimidazoles [1-M (M = Re, Fe)] also increases the antimalarial activity.A new series of organometallic benzimidazoles containing the cyrhetrenyl and ferrocenyl fragments have been synthesized and characterized. Biological evaluation against the CQ susceptible-strain (3D7) and the CQ resistant-strain (W2) of Plasmodium falciparum indicates that the cyrhetrene conjugates are more active than their ferrocenic analogs.Display Omitted
Keywords: Plasmodium falciparum; Antimalarial; Resistance; Cyrhetrene; Ferrocene; Benzimidazoles;

New photocatalyst for the degradation of organic dyes based on [Co2(1,4-BDC)(NCP)2]n·4nH2O by He-Yi Sun; Chun-Bo Liu; Yao Cong; Min-Hong Yu; Hong-Ye Bai; Guang-Bo Che (130-134).
One metal–organic framework, [Co2(1,4-BDC)(NCP)2]n·4nH2O (1) (1,4-H2BDC denotes benzene-1,4-dicarboxylic acid, HNCP denotes 2-(4-carboxyphenyl)imidazo(4,5-f)(1,10)phenanthroline), has been hydrothermally synthesized and characterized via single crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis and diffuse-reflectance UV–vis spectrum study. Compound 1 shows a 2D layer structure, which is further extended into a 3D supramolecular network structure through π–π stacking interactions. The photocatalytic study on compound 1 indicates that it is an active catalyst for the degradation of orange G, rhodamine B, methylene blue and methyl violet.One CoII metal–organic framework with distinct structures based on a 1,4-H2BDC and HNCP ligands has been hydrothermally synthesized. The behaviors of the title compound as the catalyst in photodegradation of organic dyes were also investigated.Display Omitted
Keywords: Cobalt(II) compound; 3D supramolecular structure; Photocatalyst; Degradation; Organic dyes;

Two new quaternary selenostannates (1,4-dabH)2MnSnSe4 (1) (1,4-dab = 1,4-diaminobutane) and (1,4-dabH2) Cu2SnSe4 (2) were prepared under solvothermal conditions. Compound 1 consists of one-dimensional straight anionic chains composed of alternating SnSe4 and MnSe4 tetrahedra sharing common edges. The chains are directed along [001] and surrounded by the organic cations. In compound 2 SnSe4 tetrahedra are joined by CuSe3 triangles to form a one-dimensional anionic [Cu2SnSe4]2 − chain. The central motifs of the chain are distorted Cu4Se4 and Cu2Sn2Se4 cubes sharing common faces. Four edges of the former cube are capped by two Sn and two Se atoms whereas the latter cube is capped by two Cu and two Se atoms. Both compounds were characterized by UV/Vis and IR spectroscopies as well as elemental analysis.Two new quaternary selenostannates synthesized under solvothermal conditions: Crystal structure and reflectance spectra of (1,4-dabH)2MnSnSe4 and (1,4-dabH2) Cu2SnSe4. In compound (1,4-dabH2) Cu2SnSe4, SnSe4 tetrahedra are joined by CuSe3 triangles to form a one-dimensional anionic [Cu2SnSe4]2- chain.Display Omitted
Keywords: Solvothermal synthesis; Quaternary selenostannates; Crystal structure;

A new cerium–adipate metal–organic framework [Ce(C6H8O4)(H2O)2(NO3)] was grown by simple gel diffusion technique at room temperature. The compound possesses a two dimensional network structure constructed from edge sharing CeO6(H2O)2(NO3) polyhedron. The adjacent polyhedrons are connected by the carboxylate ligand forming the 2D framework with bullet shaped channels running parallel to c axis. Thermal decomposition of the compound takes place in four steps and CeO2 is obtained as the final product. UV–visible spectra, solid state photoluminescence, and magnetic susceptibility measurements were also carried out at room temperature.A new cerium–adipate metal–organic framework [Ce(C6H8O4)(H2O)2(NO3)] was grown by simple gel diffusion technique at room temperature. The compound possesses a two dimensional network structure constructed from edge sharing CeO6(H2O)2(NO3) polyhedron. The adjacent polyhedrons are connected by the carboxylate ligand forming the two dimensional framework.
Keywords: Metal–organic frameworks; Gel diffusion technique; 2D porous structures; Bullet shaped channels; Solid state photoluminescence; Magnetic susceptibility;

An asymmetrically connected hexanuclear DyIII 6 cluster exhibiting slow magnetic relaxation by Soumya Mukherjee; Abhijeet K. Chaudhari; Shufang Xue; Jinkui Tang; Sujit K. Ghosh (144-148).
A new hexanuclear dysprosium(III) cluster [Dy6(L)7(HL)(MeOH)2(H2O)(OH)2(OAc)] (1) has been synthesized from the schiff base ligand o-phenolsalicylimine and dysprosium nitrate. This unique DyIII 6 cluster, constituted of an exclusive combination of two vertex-sharing and one edge-sharing high-anisotropy Dy3 triangles assembled together forming an unprecedentedly asymmetric homometallic DyIII 6 core, shows slow relaxation of the magnetization.A typically asymmetric new hexanuclear Dy6 complex, constituted of an unique amalgamation of two high-anisotropy Dy3 triangles exhibits Slow Relaxation of the Magnetization.Display Omitted
Keywords: Dysprosium; Cluster compounds; Asymmetry; Slow magnetic relaxation;

Anion sensing properties of gold(I) thiolate complexes bearing urea groups: Synthesis, characterization, and photophysical studies by Cheng-Luan Li; Qi-Rui Guan; Xue-Chan Li; Jin Wang; Yu-Peng Zhou; David G. Churchill; Hsiu-Yi Chao (149-151).
A series of gold(I) thiolate complexes with urea units have been synthesized and characterized: Cy3PAuSC6H4-4-NHC(O)NHC6H4-R-4 (R = Cl (1), H (2), OCH3 (3); PCy3 = tricyclohexylphosphine). Their photophysical properties, as well as anion sensing properties in CHCl3, have been studied.Three gold(I) thiolate complexes with urea units, Cy3PAuSC6H4-4-NHC(O)NHC6H4-R-4 (R = Cl (1), H (2), OCH3 (3); PCy3 = tricyclohexylphosphine), have been synthesized. Their photophysical properties as well as anion sensing properties in CHCl3 have been studied.Display Omitted
Keywords: Anions; Gold; Luminescence; Thiolate; Urea;

A series of metal–salen coordination compounds (where M is Cu2 + or Ni2 +, and the salen ligands contain various thiophene moieties) have been designed, synthesized and characterized. Both one-photon and two-photon absorption (2PA) properties have been investigated. Non-degenerate 2PA (ND-2PA) and open-aperture Z-scan measurements indicate that several of the complexes exhibit 2PA in the wavelength range of 600–700 nm with sizable 2PA cross-sections (σ2PA) of 900–2200 GM.The 2PA properties of the complexes gradually increase when the number of the thiophene moieties increases due to the extension of both the conjugation length and the donating strength.Display Omitted
Keywords: Metal–salen compounds; Thiophene moieties; Synthesis; Two-photon absorption;

A host–guest complex has been formed between cationic tetrakis(4-pyridyl)porphyrin species of (H6TPyP)4 +  ⋅ 4Cl and TMeQ[6] depending on hydrogen bonding interaction. Single crystal X-ray diffraction analysis clearly reveals the supramolecular nature of this novel TMeQ[6]-(H6TPyP)4 +  ⋅ 4Cl host–guest compound, representing the first example of structurally characterized cucurbit[n]uril-porphyrin host–guest complexes. Due to the three dimensional porous framework, the iodine adsorption behavior of this cucurbit[n]uril-porphyrin supramolecular structure has also been studied.A host–guest complex has been formed between cationic tetrakis(4-pyridyl)porphyrin species of (H6TPyP)4 +  ⋅ 4Cl and TMeQ[6] depending on hydrogen bonding interaction. Single crystal X-ray diffraction analysis clearly reveals the supramolecular nature of this novel host–guest compound, representing the first example of structurally characterized cucurbit[n]uril-porphyrin host–guest complexes.Display Omitted
Keywords: Porphyrin; TMeQ[6]; Host–guest complex; Organic molecular porous material;

A di-thiocyanato bridged dimeric copper(II) compound has been synthesized using Cu(ClO4)2 and a tridentate Schiff base ligand H2L. During compound formation, ligand H2L has been thiocyanated at the 4 position of the aromatic ring. The X-ray diffraction study confirms the nucleophilic thiocyanation of aryl ring.A di-thiocyanato bridged dimeric copper(II) compound has been synthesized and characterized by X-ray crystallography. The ligand is thiocyanated at the 4 position of the aromatic ring during compound formation. The synthesis and characterization of the compound report an efficient and novel method for nucleophilic thiocyanation of activated aromatic compounds.Display Omitted
Keywords: Copper(II); Schiff base; Nucleophilic thiocyanation; 1,3-Bridged thiocyanate; Dimer;

Homochiral iron(II) complexes based on imidazole Schiff-base ligands: Syntheses, structures, and spin-crossover properties by Zhi-Guo Gu; Chun-Yan Pang; Dan Qiu; Jie Zhang; Ju-Li Huang; Long-Fang Qin; An-Qi Sun; Zaijun Li (164-168).
A pair of mononuclear iron(II) enantiomeric complexes: fac-Λ-[Fe(R-L)3](BF4)2·MeCN (1) and fac-Δ-[Fe(S-L)3](BF4)2·MeCN (2) [L = 1-phenyl-N-(1-methyl-imidazol-2-ylmethylene)ethanamine] have been synthesized and characterized. X-ray crystallography reveals that iron(II) center is surrounded by three bidentate ligands defining a pseudooctahedral [FeN6] coordination environment. R-L ligand induces the fac-Λ isomer, while S-L ligand induces the fac-Δ isomer. Magnetic measurements reveal that both of them display obviously spin-crossover behavior at 365 K. After desolvation, they exhibit a reversible spin transition with a small hysteresis loop of ca. 3 K appearing at about T 1/2↑ = 222 K and T 1/2↓ = 219 K.Two new homochiral iron(II) enantiomeric complexes have been synthesized and characterized. Magnetic measurements reveal that both of them display obviously spin-crossover behavior at 365 K. After desolvation, they exhibit a reversible spin transition with a small hysteresis loop appearing at about T 1/2↑ = 222 K and T 1/2↓ = 219 K.Display Omitted
Keywords: Homochiral; Iron(II); Spin-crossover; Hysteresis loop;

A new coordination polymer of {[Zn2(odpa)(IP)]·4H2O}n (1) (H4odpa = 3,3′,4,4′-oxydiphthalic acid and IP = 1-H-imidazo[4,5-f][1,10]-phenanthroline), is reported. The 3D (4,6)-connected {44∙62∙88∙12}{44∙62} topology net is formed by IP and odpa ligands in 1. Interestingly, the IP ligand acts as a tridentate mode and extends the resulting 3D feature. The luminescence study indicates that the title compound emits bright red fluorescence.Display Omitted
Keywords: Luminescence; Topology; Co-ligand;

Synthesis, structure and magnetic characterization of the first azido bridged heterotetranuclear chromium-sodium complex by Hassan Hosseini-Monfared; Rahman Bikas; Milosz Siczek; Tadeusz Lis; Ritta Szymczak; Pavlo Aleshkevych (172-175).
The first mixed-metal azido bridged complex of Cr(III)–Na(I) has been prepared and its structure is determined. Reaction of chromium(III) chloride and sodium azide with bis-[(E)-N′-(1-(pyridin-2-yl)ethylidene)]carbohydrazide (HL) produced the tetranuclear complex [Cr2Na2(L)2(CH3OH)2(μ-N3)4(N3)2] (1) in good yield. The structure is composed of idealized octahedral [CrIII(N5O)] cores linked to the octahedral [Na(N4O2)] cores by two bridging azide ligands. Magnetic properties and EPR of 1 were also studied.Structure, magnetic properties and EPR of the first mixed-metal azido bridged complex of Cr(III)–Na(I) are reported.Display Omitted
Keywords: Heterotetranuclear; Carbohydrazide; Azide; Structure; Magnetic properties;

Synthesis and characterization of platinum(II) oligopyridine-peptide conjugates by Rodanthi Kaskafetou; Manolis J. Manos; Achilleas Garoufis (176-180).
Complexes of the general formulae [Pt(trpy)(cpy)]NO3, where cpy = pyridine-2-carboxylic acid, pyridine-3-carboxylic and pyridine-4-carboxylic acid (1)–(3), have been synthesized and characterized. The molecular structure of (3) has been determined by X-ray single crystal diffraction. The resin-immobilized ligand Lys-Lys-4-CO-py (L) interacts with the [Pt(trpy)H2O](NO3)2 via solid phase synthesis, forming the complex [Pt(trpy)(4-CO-py-Lys1-Lys2CONH2)](NO3)4, which has been characterized by 1H NMR and mass spectrometry.Mixed ligand Pt(II) complexes with 2,2′:6′,2″ terpyridine and pyridine carboxylic acids have been synthesized and characterized. The resin-immobilized ligand Lys2-Lys1-4-CO-py interacts with [Pt(trpy)(H2O)](NO3)2, forming via solid phase synthesis the complex [Pt(trpy)(4-CO-py-Lys1-Lys2CONH2)](NO3)4.Display Omitted
Keywords: Pt(II) terpyridine complexes; Metallointercalators; Oligopyridine peptide conjugates; Crystal structure;

Cooperative assembly of coexistent lanthanide–carboxylate chain and layer in a (4,6)-connected network by You Zhang; Jun Ji; Jun-Dan Fu; Jian-Wen Cheng; Yi-Hang Wen (181-185).
A novel 3D praseodymium metal–organic framework, [Pr2L4(H2O)2]2n ·nH2O, in which the 2D layers constructed by the interweaving right- and left-handed helical lanthanide–carboxylate chains are further pillared by 1D lanthanide–carboxylate chains, has been hydrothermally synthesized employing flexible 3-(4-(carboxymethoxy) phenyl) propanoic acid (H2L) as organic ligand. Its structure presents a new (4,6)-connected topology with a Schläfli symbol of {43.63}{44.62}2{47.64.84}{48.66.8}. This complex exhibits intense characteristic emission bands of Pr3 + ions in the solid state at room temperature.A novel Pr(III) metal–organic framework, in which the 2D layers constructed by the interweaving right- and left-handed lanthanide–carboxylate helical chains are further pillared by 1D lanthanide–carboxylate chains, is reported. It is the first (4,6)-connected with {43.63}{44.62}2{47.64.84}{48.66.8} topology and exhibits intense characteristic emission bands of Pr3 + ions at room temperature.Display Omitted
Keywords: Hydrothermal synthesis; 3-(4-(Carboxymethoxy) phenyl) propanoic acid; Helical chains; Lanthanide–carboxylate chain; Photoluminescent property;

Monometallic rhenium(I) complexes as sensor for anions by Arumugam Ramdass; Veerasamy Sathish; Murugesan Velayudham; Pounraj Thanasekaran; Kuang-Lieh Lu; Seenivasan Rajagopal (186-191).
Three new tricarbonyl rhenium(I) polypyridine complexes containing amide, urea and thiourea derivatives of 2,2′-bipyridine ligands L1L3 have been synthesized, characterized and found to show significant UV–visible absorption spectral changes on the addition of anions CN, F, CH3COO and H2PO4 . These spectral changes and 1H NMR titrations of complexes 13 with anions indicate strong binding of anions with the Re(I) complexes and the binding constants are in the range of 103–105  M− 1. The strong binding is attributed to the H-bond formation/deprotonation of ―NH proton in the ligand and the selectivity of anion is in the order CN  > F  > CH3COO  > H2PO4 .Three new tricarbonyl rhenium(I) polypyridine complexes containing amide, urea and thiourea derivatives of 2,2′-bipyridine show significant UV–visible spectral changes on the addition of anions and the selectivity is in the order CN  > F  > CH3COO  > H2PO4−. The strong binding is attributed to deprotonation of -NH proton in the ligand.Display Omitted
Keywords: Anions; Re(I) complexes; Colorimetric sensor;

Lead(II) arenedisulfonate coordination polymer: Synthesis, crystal structure and properties by Li Wang; GuanFeng Li; Mengjie Liu; Dongsheng Deng; Yamei Pei; Xinyi Wang (192-194).
A new 1-D coordination polymer, {[Pb(Phen)(1,5-nds)(H2O)2]·H2O}n (1), was constructed from 1,5-naphthalenedisulfonate (1,5-nds), 1,10-phenanthroline (Phen) and Pb(CH3COO)2·3H2O with easily reachable lead sites, which can be subsequently used to promote the epoxide ring-opening reaction of epoxides and amines with remarkable catalytic activity. In addition, the thermal and luminescent properties of 1 in the solid state were also investigated.A new arenedisulfonate coordination polymer 1 with easily reachable lead sites exhibits high catalytic activity in the epoxide ring-opening reaction.Display Omitted
Keywords: Coordination polymers; Organosulfonate; Crystal structure; Epoxide ring-opening;

2D lanthanide-based pyridine-substituted triazole benzoate coordination polymers: Structure, optical and magnetic properties by Linyan Yang; Wen Gu; Jinlei Tian; Shengyun Liao; Liangliang Xin; Ming Zhang; Xiaohua Wei; Peiyao Du; Lili Shen; Xin Liu (195-199).
A series of novel lanthanide-based coordination polymers, [Ln(L)(atpa)(H2O)2]n·1.5nH2O (HL  = 4-[3-methyl-5-(pyridin-4-yl)-1,2,4-triazol-4-yl]benzoic acid, H2atpa = 2-aminoterephthalic acid and Ln = Tb(1), Dy(2), Ho(3), Er(4), Tm(5), Yb(6)) have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, optical and magnetic measurements. Compounds 16 are isomorphous, which can be described as a 2D network based on Ln2(CO2)2 units. The magnetic properties of compound 1 (Tb) show typical antiferromagnetic interaction, while compound 2 (Dy) has ferromagnetic behavior. The room-temperature photoluminescence spectra of 1 exhibit strong characteristic emissions in the visible region, whereas compounds of Dy(2), Er(4) and Yb(6) display NIR luminescence upon irradiation at the ligand band.A series of novel lanthanide-based coordination polymers have been synthesized. Compound 1 (Tb) shows typical antiferromagnetic interaction. Compound 2 (Dy) has ferromagnetic behavior. Compound 1 (Tb) exhibits strong characteristic emissions in the visible region. Compounds of 2, 4 and 6 display NIR luminescence upon irradiation at the ligand band.Display Omitted
Keywords: Lanthanide-based; Coordination polymers; Luminescent; Magnetism;

The investigated compound of {[Zn(CQ)2(H2O)2]2[Zn(CQ)2(H2O)]3}·5DMF·2H2O (1) composition (where CQ = 5-chloro-7-iodo-quinolin-8-ol, DMF =  N,N-dimethylformamide) was prepared by simple mixing of ZnCl2 and CQ. Infrared spectroscopy confirmed the presence of CQ, DMF and H2O molecules in the prepared compound. X-ray structural analysis revealed that the structure of the title compound consists of five independent Zn(II) atoms, which are coordinated by two bidentately coordinated molecules of CQ. Three of these central atoms are also coordinated by one water molecule, while the other two have two water molecules in the coordination sphere. The structure of 1 also includes five solvated DMF and two water molecules involved in thirteen hydrogen bonds, which interconnect different complex species to form four “triplets”, in the centre of which are units with hexacoordinated Zn atoms surrounded by two units with pentacoordinated Zn atoms. These triplets are linked together to chains parallel with the b axis by two kinds of π–π interactions.{[Zn(CQ)2(H2O)2]2[Zn(CQ)2(H2O)]3}·5DMF·2H2O (CQ is 5-chloro-7-iodo-quinolin-8-ol) was prepared. The compound was studied by IR spectroscopy and monocrystal diffraction analysis. The unique structure of the prepared compound consists of mixed type coordination polyhedra, where penta- and hexacoordinated Zn(II) atoms are present.Display Omitted
Keywords: Zinc(II); Clioquinol; Crystal structure; Infrared spectroscopy;

A novel chain structure constructed from copper complexes and dimers based on bi-capped Keggin clusters by Ya-Bing Liu; Yan Wang; Li-Na Xiao; Yang-Yang Hu; La-Mei Wang; De-Chuan Zhao; Hai-Yang Guo; Xiao-Bing Cui; Cheng-Ling Pan; Ji-Qing Xu (204-207).
A new compound, [Cu(en)2][Cu(en)2(H2O)]2[SiMo8V6O42][Cu(en)2]·1.5H2O (1) (en = ethylenediamine), has been hydrothermally synthesized and characterized by elemental analysis, IR, ESR spectrum, TG analysis and single-crystal X-ray diffraction analysis. Compound 1 represents a 1-D zigzag chain-like structure constructed from dimeric units of bi-capped polyoxoanions {[Cu(en)2]2[Cu(en)2(H2O)]2[SiMo8V6O42]2[Cu(en)2]}6−  and transition metal coordination fragment [Cu(en)2]2 +. The adjacent chains are further interconnected into a 3-D supramolecular structure via hydrogen bonds. The magnetic susceptibility of 1 demonstrated the presence of antiferromagnetic interactions.The first double-supporting bi-capped Keggin dimeric compound, [Cu(en)2][Cu(en)2(H2O)]2[SiMo8V6O42][Cu(en)2]·1.5H2O (1) (en = ethylenediamine), has been synthesized under hydrothermal. Compound 1 exhibits a unique 1-D structure containing dimerized polyoxoanion linked by transition metal coordination fragment. The adjacent chains are further interconnected into a 3-D supramolecular structure via hydrogen bonds.Display Omitted
Keywords: Hydrothermal synthesis; Dimer; Keggin polyoxometalate; Transition metal complex; Magnetic susceptibility;

Syntheses and characterizations of two-dimensional polymers based on tetraimidazole tetraphenylethylene ligand with aggregation-induced emission property by Hong-Ling Zhang; Bo Zhao; Wei-Guan Yuan; Wei Tang; Fang Xiong; Lin-Hai Jing; Da-Bin Qin (208-212).
Two new coordination polymers [Co(TIPE)(H2O)2]·Hbtc·CH3CN·3H2O (1) and [Cd(TIPE)0.5(m-bdc)(H2O)]·CH3OH·H2O (2) (TIPE = tetra(3-imidazoylphenyl)ethylene, H3btc = 1,3,5-benzenetricarboxylate, m-H2bdc = 1,3-benzenedicarboxylate) have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analysis, IR, TGA, and PXRD. Furthermore, the luminescent properties of complexes 1, 2 and TIPE ligand have also been investigated in the solid at room temperature.Two new coordination polymers [Co(TIPE)(H2O)2]·Hbtc·CH3CN·3H2O·(1) and [Cd(TIPE)0.5(m-bdc)(H2O)]·CH3OH·H2O·(2) based on multifunctional tetradentate imidazole-type ligand containing tetraphenylethene chromophore have been well investigated. The crystal structures and luminescence properties of complexes 1 and 2 have been investigated in detail.Display Omitted
Keywords: Tetradentate imidazole-type ligand; Aggregation-induced emission; Coordination polymers; Crystal structure; Fluorescence;

Photo-luminescent hetero-tetranuclear Zn2Ln2 (Ln = Nd, Yb, Er, Gd, Eu or Tb) complexes self-assembled from the benzimidazole-based HL and bpe by Han Liu; Yao Zhang; Wei-Xu Feng; Pei-Yang Su; Guo-Xiang Shi; Zhao Zhang; Dai-Di Fan; Rong Lu; Xing-Qiang Lü; Wai-Kwok Wong; Richard A. Jones (213-216).
Through the self-assembly of the benzimidazole-based ligand HL (HL  = 2-(1H-benzo[d]imidazol-2-yl)-6-methoxyohenol) with Zn(OAc)2, Ln(NO3)3 (Ln = Nd, Yb, Er, Gd, Eu or Tb) and bpe (bpe =  trans-bis(4-pyridyl)ethylene), six hetero-tetranuclear Zn2Ln2-arrayed complexes (Ln = Nd, 1; Yb, 2; Er, 3; Gd, 4; Eu 5; or Tb, 6) are obtained, respectively. The result of their photophysical properties shows that the characteristic near-infrared (NIR) luminescence of Nd3 +, Yb3 + or Er3 + ions and visible luminescence of Tb3 + ions with emissive lifetimes in microsecond ranges have been sensitized from the excited states (1LC and 3LC) of the benzimidazole-based ligand, while due to the charge-transfer process from the ligand excited state to the Eu3 + ions, the Eu3 +-based emissions are quenched in complex 5.Series of hetero-tetranuclear Zn2Ln2 complexes [Zn2Ln2(L)4(bpe)(NO3)6] (Ln = Nd, 1; Yb, 2; Er, 3; Gd, 4; Eu 5; or Tb, 6) were synthesized and characterized. Their photophysical properties show that the characteristic near-infrared (NIR) emissions of Nd3 +, Yb3 + and Er3 + ions for 13 + and visible emissions of Tb3 + ion for 6 are sensitized from the excited states (1LC and 3LC) of the mixed ligands, while the Eu3 +-based emissions are quenched in 5 due to charge-transfer process.Display Omitted
Keywords: Zn2Ln2-arrayed benzimidazole-based complexes; Lanthanide luminescence; Sensitization and energy transfer;

Syntheses, structures and luminescence of a series of 4d–4f heterometallic coordination polymers constructed by 4,4′-oxybis(benzoicacid) by Jin-Ying Gao; Li-Mei Chang; Xia-Hua Xiong; Chu-Jun Chen; Wei-Ping Xie; Xing-Rui Ran; Shan-Tang Yue; Ying-Liang Liu; Yue-Peng Cai (217-220).
A series of Ln(III)-Ag(I) 4d–4f heterometallic coordination polymers [LnAg(oba)2(H2O)]n (Ln = Dy 1, Ho 2, Er 3) have been synthesized under hydrothermal reactions of 4,4′-oxybis(benzoicacid) (H2oba) with Ln(NO3)3  · 6H2O and AgNO3 at 180 °C. All complexes are isostructural with 3D networks expanded from 1D zigzag chains and 2D layers. In addition, the luminescent property of compound 1 was investigated in the solid-state at room temperature.The coordination mode of H2oba ligand.Display Omitted
Keywords: Coordination polymer; Hydrothermal synthesis; Luminescence;

Lanthanide coordination polymers constructed from 5-(4-pyridyl)-isophthalic acid: Synthesis, structure and photoluminescent properties by Yaguang Sun; Jian Li; Di Sun; Fu Ding; Shuju Wang; Zhenhe Xu; Zan Wang; Philippe F. Smet; Katrien W. Meert; Dirk Poelman (221-225).
Nine lanthanide coordination polymers [Ln2(pyip)3(H2O)4·DMF·3H2O]n (Ln = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho) based on the pyip2 − ligand {H2pyip = 5-(4-pyridyl)-isophthalic acid} have been synthesized under solvothermal conditions. X-ray crystallographic studies reveal that 19 are isostructural and crystallize in the triclinic system, space group P21/c, and exhibit a 3D framework. Topological analysis reveals that the 3D framework can be simplified to a uninodal 6-connected pcu alpha-Po primitive cubic type structure. Meanwhile, the luminescent properties of these nine coordination polymers in the solid state are also investigated. Especially the Eu and Tb compounds show bright red and green luminescence with luminescence lifetimes of 0.39 and 0.80 ms, respectively.Nine lanthanide coordination polymers [Ln2(pyip)3(H2O)4·DMF·3H2O]n (Ln = Ce, Pr, Nd, Sm, Eu,Gd, Tb, Dy, Ho) based on the pyip2 − ligand {H2pyip = 5-(4-pyridyl)-isophthalic acid} present a 3D framework and the pcu alpha-Po primitive cubic topology.Display Omitted
Keywords: Lanthanide coordination polymers; Crystal structure; Fluorescence;

An investigation into the reaction of cyanomethyltriethylammonium (CTA) halide salts with HgCl2 afforded into [(CTA)+(Hg3Cl4Br3)]n (1) and [(CTA)+]2 (Hg2Cl6)2 − (2). The two compounds have same propeller-like quaternary ammonium cations. The anion in compound 1 was a novel two-dimensional architecture and in compound 2 was an isolated centrosymmetrical dimer. Some C―H⋯N and C―H⋯X (X = Cl, Br) hydrogen bonds have been found in the two compounds, which assemble the cations and anions into a three-dimensional network. Variable-temperature dielectric properties have been studied for them. There was no dielectric anomaly in 1, whereas an obvious reversible dielectric anomaly was found in 2. The differential scanning calorimetric (DSC) and variable-temperature powder XRD properties have been studied for 2. The combined results showed that compound 2 has a solid–solid phase transition from crystalline to non-crystalline.Two novel compounds :[(CTA)+(Hg3Cl4Br3)]n (1) and [(CTA)+]2 (Hg2Cl6)2– (2) (CTA  = (Et3NCH2CN) are determined. 1 has a novel 2-D architecture inorganic anion. 2 undergoes a crystalline to non-crystalline phase transformation at 384 K.Display Omitted
Keywords: Mercury (II); Polymer; Dielectric; Differential scanning calorimetric; Phase transition;

Two novel lanthanide complexes, [La3(L)8(phen)(OH)(H2O)]n (1) and [Dy(L)3(EtOH)]n (2) (HL = 3,5-dichlorobenzoic acid, phen = phenanthroline), have been solvothermal synthesized and characterized by single-crystal X-ray diffraction, infrared spectroscopy, element analyses, powder X-ray diffraction and thermal gravimetric analyses. Complex 1 affords one-dimensional chains with hexanuclear La6 units which are peculiar in the coordination chemistry of La(III) and extended into a 3D supramolecular network via π–π stacking and hydrogen-bonding interactions. Whereas complex 2 gives 1D Dy chains, which are in turn bridged by double and quadruple carboxylate of L ligands and construct a 2D layer by weak hydrogen bonds. In addition, magnetic studies reveal antiferromagnetic behavior for complex 2.Two novel lanthanide complexes based on 3,5-dichlorobenzoic acid have been solvothermal synthesized and characterized. Complex 1 affords one-dimensional chains with hexanuclear La6 units which are peculiar in the coordination chemistry of La(III). Complex 2 gives one-dimensional Dy chains and displays antiferromagnetic behavior.Display Omitted
Keywords: Crystal structures; Lanthanide complexes; Solvothermal synthesis; Magnetic properties;

Synthesis, structure, thermal stability and surface photo-electric property of a novel three-dimensional Co(II) complex by Zhong-Feng Shi; Jia-Ming Li; Kun-huan He; Yan-Zhen Yin; Shu-Yun Niu; Jing Jin; Yu-Xian Chi (235-238).
A novel cobalt(II) complex [Co3(oba)3(phen)2]n(H2oba = 4,4′-oxybis benzoic acid, phen = 1,10-phenanthroline) has been synthesized by hydrothermal method and characterized by single crystal X-ray diffraction, IR, UV–vis, thermal stability and Surface Photovoltage Spectroscopy (SPS). Structural analysis indicated that the complex is a 3D structure with the trinuclear building unit of [Co3(oba)3(phen)2] bridged by the oba ligands. The SPS of complex indicates that there are positive response bands in the range of 300–600 nm showing photo-electric conversion properties. There are good relationships between SPS and UV–vis spectra.The SPS results of the complex indicated that it possessed clear photovoltaic response bands in UV–vis area (300–600 nm). This means that the complex has certain photo-electric conversion properties. And there are good corresponding relationships between SPS and UV–vis absorption spectra.Display Omitted
Keywords: Co(II) complex; Synthesis; Structure; Surface photo-electric property;

A fast and single-step synthesis of the octahedral Cu[(OHCH2CH2)2NH]6[CF3SO3]2 ionic liquid is presented for use in click chemistry. The ionic liquid effectively catalyzes the [3 + 2] cycloaddition of azides and terminal alkynes to give 1,4-disubstituted 1,2,3-triazoles regioselectively with high yields, without requiring bases, reducing agents, or inert atmospheres. The scope and catalytic activity of this ionic liquid are described herein for the first time. In addition, the present cost effective catalytic system is impressive even under stirring free conditions.A fast single-step synthesis of the octahedral Cu[(OHCH2CH2)2NH]6[CF3SO3]2 ionic liquid is presented for use in click chemistry. The ionic liquid effectively catalyzes the [3 + 2] cycloaddition of azides and terminal alkynes to give1,4-disubstituted 1,2,3-triazoles regioselectively with high yields, without requiring bases, reducing agents, or inert atmospheres.Display Omitted
Keywords: Alkynes; Copper; Cycloaddition; Homogeneous catalysis; Ionic liquid;

Unexpected transformation of mono- to bis-macrobicyclic dimethylglyoximate framework in a chloroform solution: Photochemical, MALDI-TOF MS and X-ray diffraction studies by Alexander S. Belov; Anna V. Vologzhanina; Yurii V. Fedorov; Evgenii V. Kuznetsov; Yan Z. Voloshin (242-246).
Crystallization of the 2-thiopheneboron-capped tris-dimethylglyoximate cobalt(II) clathrochelate from a crude chloroform unexpectedly gave single crystals of CoIIICoIICoIII bis-clathrochelate: in this complex, two macrobicyclic frameworks are linked by bridging Co2 + ion. The N–O distances in the donor oxime groups of these X-rayed mono- and bis-clathrochelates are governed by the nature of their capping groups (1.38 and 1.31 Å for the boron and cobalt “caps”). The average Co–N distances of the CoN6 -coordination polyhedra of an encapsulated cobalt ion strongly depend on its oxidation states (1.97 and 1.91 Å for the cobalt(II) and cobalt(III) ions). Co2 + ion is shifted from the center of this polyhedron by 0.2 Å due to the Jahn–Teller distortion, whereas Co3 + ions occupy the centers of the ligands' cavities. The geometry of the CoIIN6 and CoIIIN6 polyhedra is substantially different: due to the rigidity of the macrobicyclic tris-dioximate ligand and high Shannon radius of Co2 + ion, the corresponding clathrochelate has a TP geometry, whereas the smaller Co3 + ion causes the rotational–translation shortening of the CoN6 polyhedron with a decrease in its height h from 2.45 to 2.24 Å. The photochemical experiments with irradiation of a chloroform solution of the initial clathrochelate showed that the most probable pathway to the bis-clathrochelate includes photoinitiated radical oxidation of chloroform with air oxygen. The reactive species formed cause opening, rearrangement and re-capping of the macrobicyclic framework affording a new CoIIICoIICoIII bis-clathrochelate.Crystallization of 2-thiopheneboron-capped tris-dimethylglyoximate cobalt(II) clathrochelate from a crude chloroform unexpectedly gave the single crystals of CoIIICoIICoIII bis-clathrochelate. The most probable pathway to this bis-cage complex includes photoinitiated radical oxidation of chloroform with air oxygen leading to the reactive species that cause the opening, rearrangement and re-capping of macrobicyclic framework.Display Omitted
Keywords: Macrocycles; Cage compounds; Clathrochelates; Cobalt complexes; Ligand reactivity; Photochemistry;

Four bidentated iminopyrazolones (L 1 HL 4 H) were prepared by the reaction of 3-methyl-4-(4-methylbenzoyl)-1-phenyl-1H-pyrazol-5(4H)-one with POCl3 followed by the addition of the corresponding anilines. The reaction of less steric bulky ligands, L 1 HL 3 H, with ZnEt2 yields homoleptic zinc complexes [L2Zn] (13), respectively. However, the most steric bulky ligand, L 4 H reacts with ZnEt2 producing heteroleptic complex [L4ZnEt] which further reacts with benzyl alcohol (BnOH) giving [L4Zn(OBn)]2 (4). All of these complexes were characterized by elemental analyses, NMR spectroscopic study as well as X-ray diffraction. Experimental results indicate that complexes 13 are inactive toward the ring opening polymerization (ROP) of rac-lactide. On the other hand, complex 4 showed excellent activity in the ROP of cyclic esters such as rac-lactide, ε-caprolactone and β-butyrolactone.Zinc complexes derived from N,O-bidentate β-ketiminate pyrazolonate ligands were synthesized and characterized. 4, a zinc benzylalkoxide complex, is an active catalyst for the ring-opening polymerization of rac-lactide and ε-caprolactone giving polymers with the expected molecular weights and narrow PDIs and with effectively suppressing transesterification approved by MALDI-TOF analysis.Display Omitted
Keywords: Zinc; Lactone; Lactides; Ring-opening polymerization;

Synthesis, crystal structure and magnetic properties of a new cyanide-bridged mixed-valence copper(I)/copper(II) clathrate by Diana Visinescu; Oscar Fabelo; Catalina Ruiz-Pérez; Francesc Lloret; Miguel Julve (252-254).
A unique cyanide-bridge mixed-valence CuI/CuII clathrate of formula [CuI 2(CN)3][{CuII(tren)}2(μ-CN)](CF3SO3)2 [tren = tris(2-aminoethyl)amine] containing cyanide-bridged [{CuII(tren)}2(μ-CN)]3 + binuclear cations stacked between anionic honeycomb layered copper(I) cyanide networks, was synthesized and structurally characterized by single crystal X-ray diffraction. Variable-temperature magnetic susceptibility studies showed that the cyanide bridge mediates a strong antiferromagnetic interaction between the copper(II) centers (J  = − 160 cm− 1, the spin Hamiltonian being defined as H  = −J S A S B).A new mixed valence Cu(II)/Cu(I) ionic inclusion compound, in which cyanide-bridged [{CuII(tren)}2(μ-CN)]3 + binuclear cations are entrapped between anionic two-dimensional cyanide-copper(I) frameworks, has been obtained and structurally and magnetically characterized [tren = tris(2-aminoethyl)amine].Display Omitted
Keywords: Mixed-valence copper(I,II) complexes; Crystal structure; Binuclear complex; Cyanide bridge; Magnetic properties;

A rhodamine-B-based turn-on fluorescent sensor for biological iron(III) by Jeane Bordini; Ivy Calandreli; Gisdélia O. Silva; Kleber Q. Ferreira; Denise P.S. Leitão-Mazzi; Enilza M. Espreafico; Elia Tfouni (255-259).
Rhodenal, a turn-on fluorescent sensor for iron, derived from rhodamine-B, was synthesized and characterized. Its electronic absorption spectrum in ethanol has bands at 410 (ε = 500 cm− 1  mol− 1  L), 316 (ε = 14 × 103  cm− 1  mol− 1  L), and 272 nm (ε = 32 × 103 cm− 1  mol− 1  L), and it is pH sensitive with two pKa values (1.2 and 2.8). It reacts promptly with Fe3 +, with a pesudo-first order rate constant of 1 × 103  s− 1, with an equilibrium constant of 1.3 × 106  mol− 1  L, forming a violet complex (λmax  = 540 nm) with a fluorescent emission at 582 nm, with a higher sensitivity and selectivity compared to those of Fe2 +, Ba2 +, Al3 +, K+, Ca2 +, Ni2 +, Co2 +, Cd2 +, Cr3 +, Hg2 +, Mg2 +, Mn2 +, Na+, or Cu2 +. Biological assays with B16-F10 showed high permeability of plasma membrane to rhodenal and, according to confocal microscopy results, the fluorescent source originated from within the cell revealed iron pools within cytoplasmic and nuclear sub-compartments, making rhodenal a very good prospective Fe3 + sensor, in aqueous solution and especially for biological iron pool detection.Rhodenal is turn-on sensor which reacts with biological Fe3 + inside B16-F10 cells resulting in a fluorescent complex.Display Omitted
Keywords: Iron(III); Rhodamine-B; Rhodenal; Chemosensor; Bioimaging; B16-F10 cells;

To enhance photocatalytic activity of a new coordination polymer [Cd(dcbpyno)(bix)1.5]·2H2O (CP1) (dcbpyno = 2,2′-bipyridine-3,3′-dicarboxylate-1,1′-dioxide, bix = 1,4′-bis(imidazol-1-ylmethyl)benzene), with in-situ chemical oxidation polymerization process, polyaniline (PANI) loaded coordination polymer composite material (named as PANI/CP1), was synthesized. Under irradiation of visible light, PANI/CP1 displays more excellent photocatalytic activity and higher quantum yield than CP1.PANI loaded coordination polymer composite material, which displays excellent photocatalytic activity under visible light, was synthesized through in-situ chemical oxidation of aniline on the surface of coordination polymer.Display Omitted
Keywords: Coordination polymer; PANI; Composite material; Photocatalysis;

Rapid hydrothermal synthesis of MIL-101(Cr) metal–organic framework nanocrystals using expanded graphite as a structure-directing template by Le-Ting Yang; Ling-Guang Qiu; Sheng-Mei Hu; Xia Jiang; An-Jian Xie; Yu-Hua Shen (265-267).
Nanoscale MIL-101(Cr) metal–organic frameworks with giant pores, very large Brunauer–Emmett–Teller surface areas, and small dimensions in the nanoscale regime, were synthesized in high yields by an expanded graphite (EG)-templated hydrothermal strategy. Compared with a conventional hydrothermal method, the size of the MIL-101(Cr) crystals can be well controlled at nanoscale and the reaction time can be largely shortened from 8 to 2 h using such an EG-templated hydrothermal method. The size of the MIL-101(Cr) crystals can be well controlled and the synthesis cycle can be largely shortened for many practical applications.We present here the rapid hydrothermal synthesis of MIL-101(Cr) MOF nanocrystals through a reaction between chromium (III) nitrate, terephthalic acid and expanded graphite by choosing expanded graphite (EG) as a structure-directing template. Significantly, the nanosized MIL-101(Cr) crystals can be produced using EG in 2 h, while a conventional hydrothermal method needs 8 h in the absence of EG under the same hydrothermal conditions.Display Omitted
Keywords: MIL-101(Cr); Expanded graphite; Hydrothermal synthesis; Rapid synthesis; Nanoscale;

RETRACTED: Above room-temperature performance of the molecular ferroelectric: Bis(imidazolium) l-tartrate by Zhihua Sun; Shuquan Zhang; Chengmin Ji; Shigeng Li; Xiaojun Shi; Junhua Luo (268-272).
This article has been retracted at the request of the authors.

A turn-on and reversible Schiff-base fluorescence sensor for Al3 + ion by Cheng-Yi Lu; Yen-Wen Liu; Pei-Ju Hung; Chin-Feng Wan; An-Tai Wu (273-275).
A simple Schiff-base receptor 1 was prepared. It exhibits an “off-on-type” mode with high sensitivity in the presence of Al3 +. The receptor 1 exhibited a high association constant with submicromolar detection for Al3 + in EtOH–H2O (95:5 v/v) solution. The addition of EDTA quenches the fluorescence of receptor 1·Al3 + complex offering receptor 1 as a reversible chemosensor.Receptor 1 exhibits an “off-on-type” mode with high sensitivity in the presence of Al3 + and a high association constant with submicromolar detection for Al3 + in EtOH–H2O (95:5 v/v) solution.Display Omitted
Keywords: Chemosensor; Fluorescence; Turn-on; Schiff-base;

Two new isostructural tetranuclear Ag(I) complexes, formulated as [AgX(Dpq)]4 (X  = I, 1; Br, 2; Dpq = dipyrido[3,2-f:2,3-h]-quinoxaline), were synthesized by slow diffusion method for the first time. The central portion of each structure consists of a (AgX)4 core and is surrounded by four Dpq ligands. The Dpq units in the tetrameric structures are found to stack in almost parallel and display π–π stacking interactions. Moreover, Ag–Ag interactions are observed in both complexes (3.1505(7) Å for 1 and 3.1136(7) Å for 2). Density functional theory and time-dependent density functional theory calculations at the B3LYP/LanL2DZ* + 6-31G* level were performed on 1 and 2 to rationalize their experimental absorption spectra. Both complexes exhibit intense luminescence in ethanol solution at room temperature.Two new tetranuclear Ag(I) complexes with Dpq ligands have been obtained. The central portion of each structure consists of a Ag4 core and is surrounded by four Dpq ligands. π–π stacking interactions are found between Dpq ligands. The two Ag-complexes present short Ag–Ag separation.Display Omitted
Keywords: Tetranuclear Ag(I) complexes; Crystal structure; Fluorescence; DFT calculation;

A new class of thiocyanate-free cyclometalated ruthenium(II) complexes [Ru(dcpq)2(C^N)]Cl (where dcpq is 4-carboxy-2-(4′-carboxypyridin-2′-yl)quinoline and C^N is a bidentate cyclometalating ligand) (FT22 and FT61) was synthesized as near-infrared (IR) sensitizers for dye-sensitized solar cells (DSSCs). Modification of the ligand improves photovoltaic performance, and DSSCs sensitized with FT61 show large photocurrents (> 21 mA cm− 2) as well as a 55% incident photon-to-current conversion efficiency (IPCE) at 800 nm and 25% IPCE at 900 nm. The complexes exhibit superior light-harvesting properties in the near-IR region.A new class of thiocyanate-free cyclometalated ruthenium(II) complexes was synthesized as near-IR sensitizers for DSSCs. FT61-based cells show large photocurrents as well as a superior light-harvesting properties in the near-IR region.Display Omitted
Keywords: Cyclometalated ruthenium(II) complex; Pyridylquinoline; Dye-sensitized solar cell; Near-IR sensitizer;

Catalytic oxidation of cyclohexene (organic layer) at 25 °C in a stirred two phase system with fresh [Fe(OH2)6](ClO4)3/H2O2 in the pH range 2.0–4.0 (I = 0.1 M, NaClO4/HClO4) is complete within a 2-minute sampling time before deactivating in contrast to previous reports in the literature. Cyclohexene epoxide is a significant product alongside the more dominant allylic oxidation products; 2-cyclohexen-1-ol and 2-cyclohexen-1-one. Both epoxide and the accompanying allylic products appear over the same time period suggesting that they derive from the same catalytic species. The pH dependence of oxidation product yield (optimizing at ~ pH 3) suggests that the active catalyst derives from reactions involving [Fe(OH2)5OH]2 + (pKa 2.54) and is most likely the hydroperoxo ion [Fe(OH2)5OOH]2 +. Yields of cyclohexene epoxide are independent of the presence of dioxygen suggesting that an activated form of H2O2 ([Fe(OH2)5OOH]2 +) is responsible. Reduction in the relative yield of the two allylic oxidation products in the absence of dioxygen suggests that they derive from 2-cyclohexen-1-peroxy radicals resulting from iron(II)-promoted Fenton chemistry following homolytic Fe―O or O―O cleavage on [Fe(OH2)5OOH]2 +. A mechanism for the epoxide formation is proposed involving H3O+-assisted heterolytic O―O cleavage on [Fe(OH2)5OOH]2 + accompanying O atom transfer to the cyclohexene double bond. Accompanying catalysis of H2O2 decomposition persists over several hours. For the first time in a Fenton-like system evidence has been obtained for different timescales for the catalysis of oxidation reactions versus catalysis of H2O2 decomposition.A short lived iron(III)-peroxo species capable of catalyzing epoxidation and allylic oxidation on cyclohexene is formed within 2 min following addition of fresh solutions of [Fe(OH2)6]3 + to a 50-fold excess of H2O2 in mildly acidic solution (pH ~ 3). Accompanying catalysis of H2O2 decomposition is slower, persisting over several hours.Display Omitted
Keywords: Fenton; Iron(III); Hydrogen peroxide; Cyclohexene; Epoxidation; Allylic oxidation;

Three isomorphic coordination complexes constructed by flexible 1,2,4-triazole-1-acetate with the assistance of halogen or pseudohalogen anions, and [Mn(L)Cl] n (1), [Co(L)(N3)] n (2) and [Ni(L)(N3)] n (3) (L  = 1,2,4-triazole-1-acetate) have been synthesized and structurally characterized. It is interesting that the linkages of the halogen anions in 1 are the same as those of the pseudohalogen anions in 2 and 3. Single crystal structure analysis indicated a novel 4,6-connected binodal net with Schläfli {3;42;53}{32;43;55;63;72} was formed in these complexes. Dominating antiferromagnetic interactions between the metal ions were detected in these complexes, furthermore evident spin canting presented in 1 and 3 for Dzyaloshinski–Moriya (D–M) interactions.Three new coordination complexes with triazole heterocyclic ligand bearing acetic acid group have been synthesized and structurally characterized. The chloride anions in 1 are replaced by azido anions in 2 and 3 and the three complexes show novel 4,6-connected binodal net. Complexes 1 and 3 are canted antiferromagnets oriented from Dzyaloshinski–Moriya (D–M) interaction.Display Omitted
Keywords: Halogen; Pseudohalogen; Dzyaloshinski–Moriya (D–M) interactions; Metal-azide; Magnetic properties;

Synthesis, characterization and weak ferromagnetic coupling in [Cu23-CO3)(SCN)2(py)4]n by A. Vakulka; E. Goreshnik; Z. Jaglicic; Z. Trontelj (295-296).
The crystal structure of a novel [Cu23-CO3)(SCN)2(py)4]n complex has been determined. It comprises of [Cu―CO3 ―Cu]n infinite chains, running along the a-axis, and is in this aspect similar to the previously described [Cu(CO3)(4-aminopyridine)2]·H2O complex. The FTIR spectrum of [Cu23-CO3)(SCN)2(py)4]n has been recorded and analyzed. A Cu―CO3 ―Cu intrachain coupling between Cu(II) atoms has been found to be responsible for the weak ferromagnetic properties of [Cu23-CO3)(SCN)2(py)4]n.A Cu―CO3 ―Cu intrachain coupling between Cu(II) atoms has been found to be responsible for the weak ferromagnetic properties of [Cu23-CO3)(SCN)2(py)4]n.Display Omitted
Keywords: Copper(II) carbonate complex; Magnetic susceptibility; Ferromagnetic properties; 1D intrachain spin coupling;

An unprecedented Mn-containing polymer, namely, [Mn2 IIMn2 III(O2N-bta)(O2N-ipa)2(im)(OH)(H2O)2] (1) (O2N-H3bta = 5-nitro-1,2,3-benzenetricarboxylic acid, O2N-H3ipa = 2-hydroxy-5-nitroisophthalic acid, im = imidazole), has been hydrothermally synthesized by one-pot method with O2N-bta and in situ generated O2N-ipa and im ligands. Single crystal X-ray diffraction study reveals that compound 1 is constructed by tetranuclear mixed-valent MnII/MnIII clusters and exhibits a novel 2D framework. In addition, the magnetic properties and thermal stability of 1 were also discussed.A novel Mn-containing coordination polymer which is constructed by tetranuclear mixed-valent MnII/MnIII clusters has been synthesized under hydrothermal condition. The O2N-bta3 − and in situ generated O2N-ipa3 − anions exhibit the – ABAB′ – stacking mode in the 2D layer.Display Omitted
Keywords: Mn-containing polymer; 5-nitro-1,2,3-benzenetricarboxylic acid; In situ; Antiferromagnetic;

Hydrothermal reactions of CdSO4 with tetrakis(4-pyridyl)cyclobutane (tpcb) and 1,3-benzenedicarboxylic acid (1,3-H2BDC) or 5-nitro-1,3-benzenedicarboxylic acid (5-NO2-1,3-H2BDC) resulted in the formation of two coordination polymers [Cd(tpcb)0.5(1,3-BDC)]n (1) and {[Cd2(tpcb)(5-NO2-1,3-BDC)2(OH2)2] · 4H2O}n (2), respectively. Compounds 1 and 2 were characterized by elemental analysis, IR, powder X-ray diffraction, and single-crystal X-ray diffraction. 1 and 2 exhibit two different types of two-fold interpenetrating 3D architectures with (66)2(64  · 82) and (52  · 8)(54  · 6∙8)(4 · 53  · 62  · 7 · 82  · 10) Schläfli symbols, respectively. Their thermal and photoluminescent properties were also investigated.Two Cd(II) 3D coordination polymers [Cd(tpcb)0.5(1,3-BDC)]n and {[Cd2(tpcb)(5-NO2-1,3-BDC)2(OH2)2] · 4H2O}n were generated from hydrothermal reactions of CdSO4 with tetrakis(4-pyridyl)cyclobutane (tpcb) and 1,3-benzenedicarboxylic acid (1,3-H2BDC) or 5-nitro-1,3-benzenedicarboxylic acid (5-NO2-1,3-H2BDC). These complexes were structurally characterized by elemental analysis, IR, and X-ray crystallography and their thermal and luminescent properties were studied.Display Omitted
Keywords: Cadmium(II); Coordination polymer; Tetrakis(4-pyridyl)cyclobutane; 1,3-Benzenedicarboxylic acid (1,3-H2BDC); Hydrothermal reaction; Crystal structure;

Two new alkaline earth metals coordination polymers, namely, [Sr(C9NO4H7)(H2O)2] 1 and [Ba(C9NO4H7)(H2O)2] 2 have been constructed under solvothermal conditions, employing 2, 6-dimethylpyridine-3, 5-dicarboxylic acid (H2MPDC) as organic ligand. Both the two compounds have been characterized by thermogravimetric analysis, IR spectroscopy, elemental analysis and single-crystal X-ray diffraction analyses. The results of crystal structural analysis indicate that compound 1 shows infinite chains which extend into two-dimensional (2D) sheets by μ 4-MPDC2 −. Compound 2 is also a 2D layer structure and in the intralayer regions parallel left- and right-handed helical chains exist. In addition, compounds 1 and 2 exhibit strong phosphorescent emissions in the solid state at room temperature.Structural view of the coordination polymer [Ba(C9NO4H7)(H2O)2] (2). For compound 2, the [BaO8] units are connected with μ 5-MPDC2 − ligands to form an interesting chiral helical chain, and the adjacent chiral helical chains are further connected by the μ 5-MPDC2 − bridges to form a 2-D layer.Display Omitted
Keywords: Coordination polymer; 2, 6-Dimethylpyridine-3, 5-dicarboxylic acid; Alkaline earth metals; Layer; Luminescence properties;

Aminoquinoline-based fluorescent probe for detection of Cu2 + and hydrogen sulfide by Liangwei Zhang; Jinyu Sun; Shudi Liu; Xuemei Cui; Weishuang Li; Jianguo Fang (311-314).
Diethyl 2,2′-(2-oxo-2-(quinolin-8-ylamino)ethylazanediyl) diacetate (DOQED), an aminoquinoline-based fluorescent probe, was synthesized, and successfully applied in detection of Cu2 + and S2 − in an aqueous buffered solution. The emission signal of DOQED was selectively quenched by Cu2 +, and was exclusively recovered by subsequent addition of S2 −. The formation of a [Cu(DOQED)]2 + complex was confirmed by X-ray crystallography.The aminoquinoline-based probe DOQED displays good selectivity and sensitivity in detection of Cu2+ and S2– in an aqueous solution. The emission signal of DOQED was selectively quenched by Cu2+, and exclusively recovered by the addition of S2–. The formation of a Cu-DOQED complex was confirmed by X-ray crystallography.Display Omitted
Keywords: Fluorescence probe; Aminoquinoline; Copper (II); Hydrogen sulfide;

Four new complexes, [Mn2(L-H)2Cl4]·CH3CN (1), [Mn(L-H)(NO3)2·CH3OH] (2), [Ni(L-H)2](NO3)2·2H2O (3) and [Zn(L-H)L](NO3) (4) have been synthesized by the reaction of (E)-3-chloro-6-[2-(pyrazin-2-ylmethylene)hydrazinyl]pyridazine (HL) with MnCl2, Mn(NO3)2, Ni(NO3)2 and Zn(NO3)2. Noteworthy, complex 4 is a semi-deprotonated compound. The results signify that the feature of metal salt, such as the size, shape, coordination ability and coordination mode, has significant effects in determining the resulting structure. The magnetic property of 1 and antioxidant activities of HL and 14 were also studied.Three protonated complexes [Mn2(L-H)2Cl4]·CH3CN (1), [Mn(L-H)(NO3)2  · CH3OH] (2), [Ni(L-H)2](NO3)2  · 2H2O (3) and one semi-deprotonated complex [Zn(L-H)L](NO3) (4) derived from a schiff base ligand (E)-3-chloro-6-[2-(pyrazin-2-ylmethylene)hydrazinyl]pyridazine, have been synthesized and evidenced by X-ray single diffraction and elemental analyses. The magnetic property of 1 and antioxidant activities of HL and 14 were also studied.Display Omitted
Keywords: Schiff base; Deprotonation; Magnetic property; Antioxidant activity;

The first coordination polymer with distinct paired layers by Jian Cui; Khloud Alramadan; Dongsheng Li; Jack Y. Lu (318-320).
The first coordination polymer with two distinct two-dimensional layers has been synthesized and characterized [(H2O)Cu(IN)2(BPY)Cu(IN)2] 1 (IN = isonicotinate; BPY = 4, 4′-bipyridine). The entire length of the BPY molecule with “free” nitrogen cap in Cu1 layer penetrates through the parallel neighboring Cu2 layer, with half of the BPY shown above the penetrated Cu2 layer, forming a male–female paired layer network.The coordination polymer with two distinct two-dimensional layers has been synthesized. The BPY molecule with “free” nitrogen cap penetrates through the parallel neighboring layer, forming a paired layer network. The unique one-side penetrating male-female paired structure displays attractive features such as double layer robust in-plane bonding and weak inter-planar forces.Display Omitted
Keywords: Paired layers; Two-dimensional; Coordination polymers; Polythread; Interdigitation;

A new 1D Pb(II) coordination polymer, {[Pb(Hbidc)(phen)]·H2O}n (1), has been synthesized by a solvothermal method based on 1H-benzimidazole-5,6-dicarboxylato (H3bidc) and 1,10-phenanthroline (phen). Complex 1 features two types of helical chains, a 1D left- and right-handed double-stranded helical chain and a supramolecular helical chain, which interweave into a new (3,3,6)-connected achiral 3D supramolecular network. Notably, the supramolecular helical chains are induced by the different spatial orientations of the 1D double-stranded helical chains. The structure and properties of 1 have been determined by single crystal X-ray diffraction, powder X-ray diffraction (PXRD), elemental analysis (EA), thermogravimetric (TG) analysis and solid state fluorescence spectra.A 1D Pb(II) coordination polymer, {[Pb(Hbidc)(phen)]•H2O}n, shows a unique chirality induction and transfer from 1D double-stranded helical chain to 1D supramolecular helical chain. The (3,3,6)-connected achiral 3D supramolecular network is constructed and stabilitied by hydrogen bonds and ππ stacking interactions. Solid state fluorescence property of 1 has been determined.Display Omitted
Keywords: Coordination polymer; Helical chain; Hydrogen bond; Fluorescence;

The aqueous solution reaction of chelidamic acid (H3CAM), succinic acid, CdCl2·2.5H2O in the air at 50 °C, along with little of ammonia added dropwise, gave rise to colorless crystals {Cd2.5(CAM)(HCAM)(H2O)7·1.5H2O}n (1), which presents an interesting (4,6)-connected 3D structure. Notably, 1 is the third homonuclear 3D framework based on H3CAM ligand, which acts as two different μ 4/μ 5-bridges in 1 and was abbreviated to HCAM2 − and CAM3 −, respectively, in writing molecular formula of 1. Polymer 1 exhibits strong blue photoluminescence at room temperature.The third homonuclear 3D framework {Cd2.5(CAM)(HCAM)(H2O)7  · 1.5H2O}n (1) based on chelidamic acid, which presents two different μ 4/μ 5 coordination modes in 1 and is abbreviated to HCAM2 − and CAM3 −, respectively, in writing molecular formula. Polymer 1 adopts an unusual (4,6)-connected 3D topology with the Schläfli symbol (44.62)(44.610.8)2.Display Omitted
Keywords: Chelidamic Acid; (4,6)-Connected; Photoluminescence;

Monospiro- and dispirocyclic cyclotriphosphazenes, 2a and 2b, were synthesized by the reaction of hexachlorocyclotriphosphazene, N3P3Cl6 (1), with 2-(2-pyridylamino)phenol in the presence of base. The reactions of phosphazenes 2a and 2b with sodium (4-methyl-2-pyridyl)oxide afforded tetrakis- and bis(4-methyl-2-pyridyloxy)cyclotriphosphazenes, 3a and 3b, respectively. 31P NMR spectroscopy of 2b and 3b using d-camphorsulfonic acid as a chiral solvating agent indicated that they were racemates of the trans isomers. The trans configuration of trans-3b could also be elucidated by X-ray crystal structural analysis, which suggested that the steric demand of the 2-pyridyl group was responsible for the stereoselective formation of trans-2b. The steric demand of the 2-pyridyl group was supported by the reaction of N3P3Cl6 (1) with N,N′-bis(2-pyridyl)benzene-1,2-diamine, which only gave monospirocyclic cyclotriphosphazene 4a.The highly distereoselective formation of trans dispirocyclic cyclotriphosphazene trans-2b could be achieved by the reaction of hexachlorocyclotriphosphazene 1 with 2-(2-pyridylamino)phenol. The trans configuration of the alkoxy derivative trans-3b was elucidated by X-ray crystal structural analysis.Display Omitted
Keywords: Stereoselective synthesis; Trans dispirocyclic cyclotriphosphazene; 2-(2-Pyridylamino)phenol; X-ray crystal structural analysis;

Two new dissymmetrical Schiff-base copper(II) complexes, [(Cu2L)2(H2O)4]·(CuL)2·4H2O (1) and [Cu2L(dca)]n (2) (H3L = 1-(2-hydroxybenzamido)-2-(2-hydroxy-3-methoxybenzylideneamino)ethane), have been synthesized and characterized by IR, elemental analysis, X-ray crystal diffraction and magnetic properties. Single-crystal structural analysis shows that complex 1 contains a tetranuclear [Cu4L2(H2O)4]2 + cation, two [CuL] anions and four uncoordinated water molecules. Complex 2 is an infinite two-dimensional network structure in which the tetranuclear [Cu4L2] cations are interlinked by dicyanamide (dca) bridges in the end-to-end (μ 1,5) fashion. The magnetic properties of two complexes have been determined in the temperature range of 2.7–300 K.Two Schiff-base copper(II) complexes have been synthesized and characterized. Complex 1 contains a tetranuclear [Cu4L2(H2O)4]2+ cation, two [CuL]ˉ anions and four uncoordinated water molecules. Complex 2 is an infinite two-dimensional network structure in which the tetranuclear [Cu4L2] cations are interlinked by dicyanamide (dcaˉ) bridges in the end-to-end fashion.Display Omitted
Keywords: Polynuclear; Crystal structure; Magnetic properties;

Two new one-dimensional ternary selenides, [DBNH]4[M3Sn4Se11(Se2)2] (M = Cd (1), Hg (2); DBN = 1,5-diazabicyclo[4.3.0]non-5-ene), have been prepared under solvothermal conditions by the reactions of Sn, CdCl2/HgCl2, Se, DBN, and H2O at 160 °C for 6 days. Single crystal X-ray analyses reveal that compounds 1 and 2 are isostructural and crystallize in the monoclinic space group C2/c (for 1, a  = 22.236(4) Å, b  = 12.623(3) Å, c  = 21.756(4) Å, β  = 109.91(3)°; for 2, a  = 22.137(4) Å, b  = 12.663(3) Å, c  = 21.780(4) Å, β  = 109.48(3)°). Both compounds contain the similar wave-like ribbon (which is built up by SnSe4 tetrahedra, CdSe4/HgSe4 tetrahedra, and Se2 2 ions) and the protonated DBNH+ cations (which are located in the inter-ribbon spaces). A pseudo-3D network is formed through C–H⋅⋅⋅Se and N–H⋅⋅⋅Se hydrogen bonds with adjacent ribbons. The sharp UV-Vis absorption edges suggest band gaps of 2.13 eV for 1 and 2.18 eV for 2, respectively.Two novel one-dimensional heterometallic selenides, [DBNH]4[M3Sn4Se11(Se2)2] (M = Cd (1), Hg (2)), were solvothermally synthesized and characterized. Compounds 1 and 2 are isostructures with the wave-like ribbons, which are built up by SnSe4 tetrahedra, CdSe4/HgSe4 tetrahedra, and Se2 2 ions.Display Omitted
Keywords: Chalcogenides; Transition metal; Heterometallic; Ribbon;

Fluorescent chemosensor based-on the combination of julolidine and furan for selective detection of zinc ion by Yu Jeong Na; In Hong Hwang; Hyun Yong Jo; Seul Ah Lee; Gyeong Jin Park; Cheal Kim (342-345).
A new sensor 1-[[(2-furanylmethyl)imino]methyl]-2-hydroxyjulolidine (1) based on the combination of julolidine and furan groups was designed and synthesized as a Zn2 + selective fluorescent chemosensor. Upon treatment with zinc ions, the complexation of 1 with Zn2 + exhibited a pronounced enhancement in the fluorescence emission in methanol, while many other ions such as Mn2 +, Co2 +, Ni2 +, Cd2 +, Hg2 +, Na+, K+, Mg2 +, Ca2 +, Al3 + and Ag+, had no influence. Notably, this chemosensor could distinguish clearly Zn2 + from Cd2 +. The 1:1 binding mode of the 1-Zn2 + complex was drawn, based on UV–vis titration, fluorescence titration, Job plot and ESI-mass spectrometry analysis.A new sensor 1-[[(2-furanylmethyl)imino]methyl]-2-hydroxyjulolidine (1) based on the combination of julolidine and furan groups was designed and synthesized as a Zn2 + selective fluorescent chemosensor. Notably, this chemosensor could distinguish clearly Zn2 + from Cd2 +.Display Omitted
Keywords: Chemosensor; Zinc ion; Julolidine; Furan;

Reactions of ferrocene and (η5-cyclopentadienyl)(η4-tetraphenylcyclobutadiene)cobalt derived alkynylaldehydes with p-anisidine gave the corresponding metal sandwich based alkynylimines, 4-methoxy-N-(3-ferrocenylprop-2-ynylidene)aniline and 4-methoxy-N-[3-(η5-cyclopentadienyl)(η4-tetra-phenylcyclobutadiene)cobalt prop-2-ynylidene]aniline. The 1,4-nucleophilic addition of sodium methylmalonate with these alkynylimines gave the first examples of metal sandwich substituted 2-pyridones, [methyl 1-(4-methoxyphenyl)-2-oxo-4-ferrocenyl 1,2-dihydropyridine-3-carboxylate and methyl 1-(4-methoxyphenyl) 2-oxo-4-(η5-cyclopentadienyl)(η4-tetra-phenylcyclobutadiene)cobalt 1,2-dihydropyridine-3-carboxylate in good yields. Reaction of sodium ethylmalonate with the ferrocene derived alkylimine gave the stable ferrocene derived 2-pyridone, ethyl 1-(4-methoxyphenyl)-2-oxo-4-ferrocenyl 1,2-dihydropyridine-3-carboxylate which was also structurally characterized.The synthesis and structural characterization of the first examples of ferrocene and cobalt sandwich substituted 2-pyridones are described. The synthesis was made possible by the facile 1,4 nucleophilic addition reaction of sodium alkyl malonate with the alkynyl imine derivative of ferrocene and (η5-Cp)Co(η4-C4Ph4).Display Omitted
Keywords: Ethynyl ferrrocene; Pyridone; Alkynyl aldehyde; Cobalt sandwich;

Three coordination polymers, [Cd(p-CPhH2IDC)(H2O)] n (p-CPhH4IDC = 2-(4-carboxylphenyl)-1H-imidazole-4,5-dicarboxylic acid) (1), [Cd3(p-CPhHIDC)2(H2O)6] n (2), and {[Cd2(p-CPhIDC)(2,2′-bipy)2]·H2O} n (2,2′-bipy = 2,2′-bipyridine) (3), have been hydrothermally synthesized, and structurally characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, and further characterized by thermogravimetric and solid-state fluorescence determinations. Polymer 1 presents a 2D doubled-layer architecture containing 1D distorted quadrilateral open channels. Polymer 2 emerges a 1D zigzag chain constructed by parallelogram clusters. Polymer 3 exhibits a net-like layer structure constructed by two types of wavy chains. The coordination features of the ligand p-CPhH4IDC have been discussed as well.Three Cd(II) imidazole multi-carboxylate-based CPs have been hydrothermally prepared and structurally characterized by single-crystal X-ray crystallography. The thermal and solid-state photoluminescence properties of the polymers have been determined as well.Display Omitted
Keywords: Imidazole multi-carboxylate; Cadmium; Polymer; Crystal structure;

Two fluorescent 2,6-substituted pyridyl boron-dipyrromethene dyes for selective sensing of cuprous ions by Lian Zhou; Cheng-Cheng Zhu; Yun-Shan Xue; Wei-Jiang He; Hong-Bin Du; Xiao-Zeng You; Yi-Zhi Li (355-359).
Two new pyridine-substituted boron-dipyrromethene (BODIPY) dyes have been synthesized via the Suzuki coupling reactions of 2,6-diiodo-1,3,5,7-tetramethyl-8-methyl-4,4-difluoroboradiazaindacene and respective pyridinylboronic acid. The molecular structures of the two title compounds have been determined by single-crystal X-ray diffraction analyses. The absorption and steady-state fluorescent properties in different solvents were investigated, which showed that the two compounds are highly fluorescent with a relatively small Stokes shift, high fluorescent quantum yields and little solvent dependence, similar to other BODIPY chromophores. The fluorescence of two compounds were highly sensitive towards Cu+, owing to significant interactions between Cu+ and the nitrogen atoms on the pyridine rings.Two fluorescent pyridine-substituted boron-dipyrromethene (BODIPY) dyes were prepared and shown to be highly selective towards Cu+.Display Omitted
Keywords: BODIPY; Fluorescence; Cu+ detection; Crystal structure; Suzuki coupling; Imaging;