Inorganic Chemistry Communications (v.46, #C)

Contents List (iii-xxiii).

A one-dimensional ribbon copper(II) complex, {CuII 3(L)2(OH)2(NO3)2(H2O)4}n (1, HL = 1-methyl-2-(3H-[1–3]triazol-4-yl)-1H-benzimidazole), has been hydrothermally synthesized from in situ generated HL at 160 °C. Its structure is very unusual that all ligands and Cu(II) ion are distributed in the same horizontal plane in each chain. Two ligands chelate and bridge two Cu(II) ions to form a planar metalloligand which is then connected to each other through coordination to another Cu(II) to give the 2 + 1 infinite chain structure. Axial coordination sites of the Cu(II) are taken up by nitrate and water. Hydrogen bonding and π–π stacking interactions between chains intensify the stability of 3D supramolecular architecture. This particular structure is the result of a cooperative effect associated with the Jahn–Teller distortion of the copper(II) ion, the hydrogen bonding and π–π stacking interactions. Its magnetic properties indicate antiferromagnetic interactions between copper(II) within the chain.A 1D coordination polymer with 2 + 1 motif, {CuII 3(L)2(OH)2(NO3)2(H2O)4}n (1, HL = 1-methyl-2-(3H-[1–3]triazol-4-yl)-1H-benzimidazole), was synthesized under hydrothermal reaction coupling with crucial in situ ligand decarboxylation. 3D supramolecular architecture was further stabilized by hydrogen bonding and π–π interactions between chains. Magnetic measurement and fitting indicate antiferromagnetic interactions between copper(II) ions within the chain.Display Omitted
Keywords: Copper(II) complex; Hydrothermal synthesis; In situ ligand formation; Magnetism;

Tris(acrylato)uranylates as a scaffold for NLO materials by Vladislav V. Klepov; Larisa B. Serezhkina; Anna V. Vologzhanina; Denis V. Pushkin; Olga A. Sergeeva; Sergey Yu. Stefanovich; Victor N. Serezhkin (5-8).
Novel uranyl acrylate complexes with general formula R[UO2(CH2CHCOO)3] (R=K+, NH4 +, Rb+, or Cs+) were synthesized and characterized by X-ray diffraction, IR spectroscopy and second harmonic generation (SHG) measurements. All four compounds are isostructural and crystallize in the non-centrosymmetric P213 space group. Acrylate anions act as bidentate chelating ligands forming [UO2(CH2CHCOO)3] complexes which are connected through electrostatic interactions with counter ions. SHG measurements revealed the inverted correlation between the Q  =  I /I SiO2 values and the radii of counter ions.Novel uranyl acrylate complexes with general formula R[UO2(CH2CHCOO)3] (R=K+, NH4 +, Rb+, or Cs+) were synthesized and characterized by X-ray diffraction, IR spectroscopy and second harmonic generation (SHG) measurements.Display Omitted
Keywords: Uranyl; Acrylate; X-ray diffraction; Non-linear optics; Infrared spectroscopy;

Carbon dioxide selective adsorption within a highly stable mixed-ligand Zeolitic Imidazolate Framework by Lin Huang; Ming Xue; Qingshan Song; Siru Chen; Ying Pan; Shilun Qiu (9-12).
A new mixed-ligand Zeolitic Imidazolate Framework Zn4(2-mbIm)3(bIm)5·4H2O (named JUC-160, 2-mbIm = 2-methylbenzimidazole, bIm = benzimidazole and JUC = Jilin University China) was synthesized with a solvothermal reaction of Zn(NO3)2·6H2O, bIm and 2-mbIm in DMF solution at 180  °C. Topological analysis indicated that JUC-160 has a zeolite GIS (gismondine) topology. Study of the gas adsorption and thermal and chemical stability of JUC-160 demonstrated its selective adsorption property for carbon dioxide, high thermal stability, and remarkable chemical resistance to boiling alkaline water and organic solvent for up to one week.A new mixed-ligand ZIF material (JUC-160) with the GIS topology shows high thermal stability, remarkable chemical resistance to boiling alkaline water and organic solvent up to one week and high CO2 selectivity sorption properties.Display Omitted
Keywords: Zeolitic Imidazolate Frameworks; Mixed ligand; Stability; Selective adsorption; Carbon dioxide;

An amine functionalized rht-type metal-organic framework with the improved performance for gas uptake by Xiao-Jun Wang; Jian Li; Pei-Zhou Li; Ling-Bao Xing; Han Lu; Hui Wu; Yanhui Shi; Ruqiang Zou; Yanli Zhao (13-16).
A dendritic hexacarboxylate ligand featuring amine and triazole groups was rationally designed and synthesized, which was employed to construct a (3,24)-connected rht-type copper(II) metal-organic framework (MOF, NTU-105-NH2 ) under solvothermal conditions. The desolvated amine-functionalized MOF demonstrated improved CO2 and H2 uptake capacity as well as significant higher selectivity towards CO2 over N2 in comparison to its parent MOF.A triazole and amine dually functionalized MOF exhibited high CO2 and H2 uptake capacity as well as high selectivity towards CO2 over N2.Display Omitted
Keywords: Metal-organic frameworks; Ligand pre-design; Gas uptake; rht-network;

A new solvothermal route to crystalline proustite Ag3AsS3 with photocatalytic properties by Rongqing Zhao; Jian Zhou; Xing Liu; Rong Li; Qiuling Tang (17-20).
A new solvothermal method has been successfully prepared crystalline proustite Ag3AsS3 (1) by the reactions of As2O3, AgNO3 and elemental sulfur in diaminopropane (dap) at 160 °C for 3 days. The crystalline material of 1 was characterized by single crystal X-ray diffraction, powder X-ray diffraction, UV–visible diffuse reflectance spectroscopy, scanning electron microscopy and nonlinear optical determination. The three-dimensional polar framework of 1 is constructed by the linkages of unsymmetrical [AsS3] trigonal pyramids and T-shaped [AgS3] units via bridging S atoms. The absorption edge of 1 is 2.03 eV, exhibiting properties of the semiconductor, and its theoretical band structure has also been studied. Photocatalytic experiments have shown the ability of 1 in the degradation of methylene blue (MB) under visible light (λ > 420 nm).A new solvothermal method has been successfully prepared crystalline Ag3AsS3 by solvothermal techniques. Photocatalytic experiments have shown the ability of Ag3AsS3 in the degradation of methylene blue (MB) under visible light (λ > 420 nm).Display Omitted
Keywords: Solvothermal syntheses; Proustite; Thioarsenates; Structure; Photocatalytic properties;

Facile synthesis of porous Pr(OH)3 nanowire bundles and their magnetic properties by Xingwang Ouyang; Shuaishuai Yuan; Qinbiao Qiu; Weiwei Zeng; Gregory A. Hope; Haohua Li (21-23).
In this work, 1D Pr(OH)3 nanowire bundles were successfully constructed on Ti substrate by electrodeposition. Moreover, the magnetic properties of Pr(OH)3 were investigated for the first time. The magnetic measurements shows the as-deposited Pr(OH)3 nanostructures exhibit ferromagnetic behavior.Pr(OH)3 have been grown on Ti substrates using a convenient template-free electrochemical deposition and their magnetic properties were studied for the first time.Display Omitted
Keywords: Pr(OH)3; Nanowire; Electrodeposition; Magnetic;

Two cadmium coordination polymers showing three-fold interpenetrated and self-catenated three-dimensional networks by Zhi Yang; Shan Zhao; Shan-Shan Han; Ling-Yun Zheng; Bao-Long Li; Bing Wu (24-28).
The hydrothermal reaction of CdCl2, 1,4-bis(2-methyl-imidazol-l-ylmethyl)benzene (bix) and fumarate (fum) or glutarate (glu) gives two unusual coordination polymers {[Cd2(bix)2(fum)Cl2]·0.5H2O}n (1) and [Cd2(bix)(glu)2]n (2). 1 shows a three-fold interpenetrated three-dimensional distorted diamondoid network with different length three ligands. 2 displays a 6-connected self-catenated three-dimensional network with the point symbol of (44•610•8) based on Cd2 dimer. The luminescence and thermal stability were investigated.The hydrothermal reaction of CdCl2, 1,4-bis(2-methyl-imidazol-l-ylmethyl)benzene, fumarate or glutarate gives two coordination polymers showing a three-fold interpenetrated 3D distorted diamondoid network and a 6-connected self-catenated 3D network.Display Omitted
Keywords: Diamondoid network; Self-catenated; Three-fold interpenetrated; Cadmium coordination polymer; Luminescence;

An inorganic–organic hybrid [tetrabutylammonium][PbI3] crystallizes in tetragonal space group I-42d, which inorganic components form one-dimensional (1D) face-sharing iodoplumbate chain. This hybrid shows a novel dielectric anomaly around 125 °C. The variable-temperature single crystal and powder X-ray diffraction (PXRD) measurements revealed that the dielectric anomaly arises from the disorder–order transformation of tetrabutylammonium. The hybrid emits orange-red luminescence, ascribed to the semiconductor emission of 1D [PbI3] chain.Inorganic–organic hybrid, [tetrabutylammonium][PbI3], with one-dimensional face-sharing iodoplumbate chain shows novel dielectric anomaly and semiconductor emission.Display Omitted
Keywords: Inorganic–organic hybrid; Iodoplumbate chain; Dielectric anomaly; Semiconductor emission;

A novel 2D inorganic–organic hybrid compound constructed from {CuMo2O7} n bimetallic oxide chains bridged by N-containing ligand by Xiang-Guang Guo; Wen-Bin Yang; Xiao-Yuan Wu; Qi-Kai Zhang; Lang Lin; Can-Zhong Lu (33-35).
A novel inorganic–organic hybrid compound [Cu(Mo2O7)(H2MDP)] (1) has been hydrothermally synthesized from the self-assembly of CuI, H2MoO4 and H2MDP ([Methylenebis(3,5-dimethylpyrazole)]). Compound 1 is constructed from one-dimensional {Cu(Mo2O7)} n bimetallic oxide chains bridged by H2MDP ligands into a novel two-dimensional hybrid compound. There exist left- and right-handed Cu―O―Mo helical chains in the bimetallic oxide chains.Here we present a novel 2D inorganic–organic hybrid compound constructed from {CuMo2O7} n bimetallic oxide chains, which contains left- and right-handed Cu―O―Mo helical chains.Display Omitted
Keywords: Hybrid compound; Hydrothermal synthesis; Bimetallic oxide chain; Helical chains;

A new noncentrosymmetric Zn(II) compound, namely [Zn4(mbdc)3(μ 4-O)(DMA)(H2O)]n  · 2n(DMA) (1, H2mbdc = isophthalic acid, DMA = N,N′-dimethylacetamide), has been solvothermally synthesized by the combination of H2mbdc and Zn(NO3)2. Single crystal X-ray analysis reveals that compound 1 is a complicated 3D framework based on isolated tetrahedral {Zn4O} clusters as building subunits, which can be simplified into a 6-connected sxb topological network. Second-harmonic generation (SHG) measurements on powder samples reveal that compound 1 exhibits moderate SHG signals approximately 1.67 times that of KDP (KH2PO4). Luminescent investigations show that compound 1 emits intense blue luminescence at room temperature.Presented here is a new noncentrosymmetric Zn(II) compound [Zn4(mbdc)3(μ 4-O)(DMA)(H2O)]n  · 2n(DMA) (1, H2mbdc = isophthalic acid, DMA = N,N′-dimethylacetamide), which features an extended 3D framework based on isolated tetrahedral {Zn4O} clusters as building subunits.Display Omitted
Keywords: Solvothermal synthesis; Tetrahedral {Zn4O} cluster; sxb topology; Luminescence;

A novel trivalent europium, Eu(III), 2,2′-bipyridine-5,5′-dicarboxylic acid (bpdc) metal–organic framework, namely, [Eu4(bpdc)6(CH3NH2)3(DMSO)(H2O)] 1 was synthesized by the solvothermal reaction of bpdc with trivalent Eu(III) salts in a mixed solvent system containing N,N′-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The single X-ray diffraction indicated that complex 1 had a novel porous three-dimensional framework with two different binuclear metal units. The photoluminescence spectrum of the complex displayed strong emission maxima at 472 and 618 nm.The complex exhibits two types of binuclear metal units, bridged together by bpdc ligands forming a 3D MOF. Additionally, the complex exhibits characteristic Eu luminescence, indicating that it is a potential light-emitting candidate.Display Omitted
Keywords: Metal organic frameworks; Lanthanide; Thermal stability; Luminescent;

Highly selective recognition of mercury ions through the “naked-eye” by Ye Won Choi; Ga Rim You; Myoung Mi Lee; Jinheung Kim; Kwang-Deog Jung; Cheal Kim (43-46).
A new sensor 2-((E)-(3-(1H-imidazol-1-yl)propylimino)methyl)-5-(diethylamino)phenol (1) based on the combination of diethylaminosalicylaldehyde and imidazole groups was designed and synthesized as a Hg2 + selective colorimetric chemosensor. Upon treatment of 1 with mercury ions, sensor 1 showed a color-change from colorless to yellow in a mixture of H2O/DMF (5:95), while many other ions such as Al3 +, Zn2 +, Cd2 +, Cu2 +, Fe2 +, Mg2 +, Cr3 +, Ag+, Co2 +, Ni2 +, Na+, K+, Ca2 +, Mn2 + and Pb2 + had no influence. Notably, this chemosensor could distinguish clearly Hg2 + from Cu2 +, Ag+, Fe2 + and Pb2 +. The underlying signaling mechanism is a ligand-to-metal charge-transfer (LMCT) process. Compound 1 showed the serial formation of the 1:1 and the 1:2 complexation between 1 and Hg2 +. This two-step binding mode was proposed based on the UV titration, 1H NMR titration and ESI-mass studies.A new sensor (1) based on the combination of diethylaminosalicylaldehyde and imidazole groups was designed and synthesized as a Hg2 + selective colorimetric chemosensor. Upon treatment of 1 with mercury ions, 1 showed a color-change from colorless to yellow in aqueous solution, while many other ions had no influence. Notably, this chemosensor could distinguish clearly Hg2 + from Cu2 +, Ag+, Fe2 + and Pb2 +.Display Omitted
Keywords: Mercury ion; Colorimetric; Chemosensor; Naked-eye detection; LMCT process;

The title compound, catena-(1,2,3,6-tetrahydropyridine tris(μ2-chloro)-cadmium(II)), has a hexagonal perovskite-type structure with formula AMX3. It undergoes a reversible dielectric transition at about 197 K. The transition was accompanied by significant dielectric anomaly, and was confirmed by DSC measurements. The variable-temperature single crystal X-ray diffraction analysis reveals that the transition is a process of the doubling of the cell volume from P21/m to P21/a. The transition is caused by the order–disorder change of the 1,2,3,6-tetrahydropyridinium cation.A phase transition compound, {[Thpy]·[CdCl3]} (1), has been synthesized. Differential scanning calorimetry measurement shows a pair of sharp peaks at 196.4 K (heating) and 183.1 K (cooling), indicating the phase transition is first-order. The phase transition is derived from the order-disorder transition of the 1,2,3,6-tetrahydropyridinium cation.Display Omitted
Keywords: Phase transition; Order–disorder; Dielectric; Perovskite-type structure;

The synthetic efficacy of thorium tetrachloride bis(dimethoxyethane), ThCl4(DME)2, is improved by adding 1,2-dimethoxyethane (DME) to the reaction mixture. The syntheses of the known metallocene dichlorides (C5Me5)2ThCl2 (1), (1,2,4- t Bu3-C5H2)2ThCl2 (2), and (C5Me4Et)2ThCl2 (3) are used to demonstrate this finding. The full characterization and X-ray crystal structure of (C5Me4Et)2ThCl2 (3) is also reported.The synthetic efficacy of thorium tetrachloride bis(dimethoxyethane), ThCl4(DME)2, is improved by adding 1,2-dimethoxyethane (DME) to the reaction mixture. The syntheses of the known metallocene dichlorides (C5Me5)2ThCl2, (1,2,4- t Bu3-C5H2)2ThCl2, and (C5Me4Et)2ThCl2 are used to highlight this finding.Display Omitted
Keywords: Thorium; Cyclopentadienyl; Chloride; 1,2-Dimethoxyethane; X-ray crystallography;

Synthesis, crystal structure, DNA binding and molecular docking studies on new copper(II) salicylate [Cu(DTBSA)2(2,2′-bpy)](dmf) by Mohan Gopalakrishnan; Kabali Senthilkumar; Priya Rajendra Rao; Ramamoorthy Siva; Nallasamy Palanisami (54-59).
A mononuclear copper(II) salicylate with bulky substitution [Cu(DTBSA)2(2,2′-bpy)](dmf) (1) (DTBSA = 3,5-di-tert-butyl salicylic acid, 2,2′-bpy = 2,2′-bipyridyl) has been synthesized and characterized with the aid of elemental analysis and infrared, ultraviolet, fluorescence and electron paramagnetic resonance spectroscopic techniques. The molecular structure of compound 1 was analyzed by single-crystal X-ray diffraction, it shows monomeric copper atom coordinating to two salicylate moieties along with one bipridyl ligand. Hydrogen bonding interactions and π–π aromatic stacking interactions led to the formation of 1D polymeric structure. The DNA binding studies of compound 1 against CT-DNA (calf thymus) investigated by absorption, emission and molecular docking methods. The results from binding constant (Kb ), linear Stern–Volmer quenching constant (Ksv ) and molecular docking have shown that the copper(II) salicylate has better binding activity.A new copper(II) salicylate [Cu(DTBSA)2(2,2′-bpy)](dmf) (1) has been synthesized and characterized. In solid state crystal packing of monomer molecules containing hydrogen bonds and π–π stacking interactions lead to form step grow 1D polymeric structure. The biological activity against CT-DNA was analyzed by UV–Vis, fluorescence and molecular docking methods.Display Omitted
Keywords: Copper(II) salicylate; Hydrogen bonding; DNA binding; Molecular docking;

Impact of metallonucleases on DNA interactions: Structural validation and in-vitro antibiogram assay by Vellaichamy Muniyandi; Narayanaperumal Pravin; Natarajan Raman (60-64).
Four novel complexes were synthesized using 2-aminobenzophenone Schiff base precursor and characterized by various analytical techniques. FT-IR results demonstrate that the Schiff base ligand, obtained by the condensation of 2-aminobenzophenone with 2-hydroxybenzaldehyde, coordinates to the metal ion via azomethine nitrogen, phenolic oxygen and carbonyl groups. Furthermore, the intercalative mode of these octahedral complexes with calf thymus (CT) DNA has been explored using absorption spectra, cyclic voltammetric and viscosity measurements. Gel electrophoresis assay demonstrates the effective cleaving aptitude of pBR322 DNA by complexes in the presence of an activating agent (H2O2). Moreover, the in-vitro biological activities of metal complexes have been screened against few pathogenic bacterial and fungal strains by well diffusion technique. It is found that all the complexes show potential activities as compared to the free ligand. These findings may lead to develop novel DNA targeting metallonucleases.The synthesized 2-aminobenzophenone based complexes exert their promising in vitro DNA binding and cleavage potency as well as they can act as anti-microbial agents. The data reveal that our complexes are dynamic DNA targets.Display Omitted
Keywords: Intercalative mode; Calf thymus DNA; Gel electrophoresis; Antimicrobial studies;

One cadmium coordination polymer with 2-Fold parallel Interpenetration Structure and Helical Chains based on biphenyl-4-hydroxyl-3,3′-bicarboxylic acid (H2L) and μ-4,4′-bipyridine (bpy) {[Cd(L) (bpy)1/2(H2O)]2} n (1), has been obtained by hydrothermal synthesis and characterized by elemental analysis, powder X-ray diffraction (PXRD), IR spectra, thermal gravimetric analyses (TGA) and also by single-crystal X-ray diffraction. It crystallizes in the monoclinic, space group P21/c. The L2 − anions of complex 1, as a bridging ligand, connect Cd(II) ions to form two-dimensional (Cd2(L)2)n layer in which the 1D (Cd–L)n helical chains are alternately arranged in a right- and left-handed sequence. These layers are further linked to build a three-dimensional network by the bpy ligands. In addition, the photochemical property of compound 1 has also been investigated.An unusual compound {[Cd(L)(bpy)1/2(H2O)]2} n (1) comprising two equivalent interwoven nets of dmc topology has been obtained by hydrothermal reactions, in which the right- and left-handed (Cd–L)n helical chains are alternately arranged to give rise to 2D bichiral helical structure.Display Omitted
Keywords: Cadmium; μ-4,4′-Bipyridine; Coordination polymer; Biphenyl-4-hydroxyl-3,3′-bicarboxylic acid;

A new acentric metal borate Mg[B6O9(OH)2]·4H2O: Synthesis, structure and optical property by Han-Qing Wu; Qi Wei; Huan He; Bai-Feng Yang; Qiang Zhang; Guo-Yu Yang (69-72).
An acentric metal borate, Mg[B6O9(OH)2]·4H2O, has been successfully made under mild hydrothermal conditions. Its structure contains a novel 2-D layer constructed from the B6O11(OH)2 cluster units, which are further linked by the MgO6 polyhedra to form a 3-D framework. It has a UV cutoff edge below 200 nm and exhibits SHG efficiency approximately 1.1 times that of KDP.A new acentric Mg[B6O9(OH)2]·4H2O has been made under mild hydrothermal conditions. Its structure contains a novel [B6O11(OH)2]n layer and is further linked by MgO6 octahedra to form a 3-D framework, showing that it is phase-matchable with SHG signal intensity approximately 1.1 times that of KDP.Display Omitted
Keywords: Borate; Cluster; Magnesium; Acentric; Nonlinear optics;

Chiral anionic binuclear zinc complexes based on diaminocyclohexane ligand and their in vitro antiproliferative studies by Mohammad Azam; Saud I. Al-Resayes; Agata Trzesowska-Kruszynska; Rafal Kruszynski; Ambarish Verma; Uttam K. Pati (73-80).
Two novel binuclear chiral anionic Zn(II) complexes, [Zn2LCl3] (C2H5)3N+ 1 and [Zn2L(CH3COO)3] (C2H5)3N+ 2 counterbalanced by triethyl ammonium cation, have been synthesized from ligand, 2,2′-((1E,1′E)-((1R,2R)-cyclohexane-1,2-diylbis(azanylylidene))bis(methanylylidene))dipheno, H2L. The ligand, H2L and its complexes are characterized by elemental analyses, IR, 1H and 13C NMR, ESI-MS, electronic and thermal studies. Complex 1 has been additionally characterized by single crystal X-ray diffraction studies and confirmed a slightly distorted tetragonal pyramid coordination environment in which both zinc atoms are five coordinated by two imine nitrogen atoms, two oxygen atoms and one chloride ion located at the polyhedron apex. Ligand, H2L and its Zn(II) complexes have been subjected to antiproliferative studies against HCT p53 wild type as well as HCT p53 null cell lines, and the results suggest complexes to be an effective antiproliferative agent against these cancer cell lines in comparison to ligand, H2L. Furthermore, DNA fragmentation studies revealed that Zn(II) complexes induce significant p53 independent apoptosis in cancer cell lines.Two structurally characterized binuclear chiral anionic Zn(II) complexes counterbalanced by triethyl ammonium cation were subjected to antiproliferative studies against HCT p53 wild type as well as HCT p53 null cell lines. Results revealed that the compounds induce significant p53 independent apoptosis in cancer cell lines.Display Omitted
Keywords: Chiral ligand; Zinc complexes; Crystal structure; Antiproliferative studies; DNA fragmentation;

Self-assembly of AgX (X  = ClO4 and PF6 ) with a C 3-tridentate ligand in EtOH/CH2Cl2 affords a ligand-eclipsed double chain whereas the cognate reaction in H2O/MeOH produces a ligand-staggered chain consisting of alternate cyclic and bridging moieties. The anion exchangeability and photoluminescence properties are significantly affected by the different skeletal structures.Self-assembly of silver(I) ion with a C 3-symmetric tridentate ligand, N,N′,N″-tris(2-pyridinylethyl)-1,3,5-benzenetricarboxamide, produces a novel eclipsed double chain and a staggered chain depending on the reaction media as template. The difference in both photoluminescence and anion exchangeability is significantly affected by the skeletal structures and the nature of counteranions.Display Omitted
Keywords: Anion exchangeability; Eclipsed and staggered double chains; Media effects; Photoluminescence; N,N′,N″-tris(2-pyridinylethyl)-1,3,5-benzenetricarboxamide;

Bulky group functionalized porphyrin and its Zn (II) complex with high emission in aggregation by Gaobin Zhang; Qiyu Chen; Yuyang Zhang; Lin Kong; Xutang Tao; Hongbo Lu; Yupeng Tian; Jiaxiang Yang (85-88).
A novel porphyrin derivative 5,10,15,20-tetra-4′-(tert-butylthio)phenylporphyrin (abbreviated as TSPP) and its Zn (II) complex (Zn-TSPP) have been synthesized and characterized, which possess aggregation-induced emission enhancement (AIEE) properties. The bulky groups increase the intermolecular steric effects which impede the π–π stacking interactions inducing J-aggregates of the two compounds in the THF-H2O mixed solution. DFT calculation was used to understand the relationship of molecular structure and luminescence.Bulky substituent modified porphyrin derivative and its Zn (II) complex possess excellent aggregation-induced emission enhancement (AIEE) properties due to the enormous intermolecular steric effects which hamper the π–π stacking interaction and induce the formation of J-aggregation, by which to achieve ACQ–AIEE transformation.Display Omitted
Keywords: Porphyrin; Fluorescence; AIEE; J-aggregate;

The research of employing polyoxometalates as pure-inorganic electron-transfer mediators on dye-sensitized solar cells by Chun-Chen Yuan; Shi-Ming Wang; Wei-Lin Chen; Lin Liu; Zhi-Ming Zhang; Ying Lu; Zhong-Min Su; Si-Wen Zhang; En-Bo Wang (89-93).
Two Keggin-type polyoxometalates [K6CoIIW12O40 (denoted as {CoIIW12}) and K5CoIIIW12O40 (denoted as {CoIIIW12})] were firstly employed as the redox couple in dye-sensitized solar cells. Photocurrent density–photovoltage curves, cyclic voltammetry curves, photocurrent action spectra and UV–vis spectra demonstrated that {CoIIW12} and {CoIIIW12} displayed weak absorption in the visible light region, potential matching with dye and TiO2 conducting band, and significant conversion efficiency.Two Keggin-type polyoxometalates have been successfully employed as the redox couple in dye-sensitized solar cells for the first time, which achieved relatively high values of open circuit voltage (651 mV) and fill factor (0.549).Display Omitted
Keywords: Polyoxometalates; Solar cells; Inorganic; Electron-transfer mediator;

A heterometallic Ni2Gd2 complex : Synthesis, structure and magnetic properties by B. Cristóvão; R. Pełka; B. Miroslaw; J. Kłak (94-97).
A novel tetranuclear complex [Ni2Gd2(L)2(CH3COO)2(NO3)2](NO3)2·6H2O·4MeOH (1) with a nitrate ion coordinating in a manner observed until now only in polymeric structures was obtained. The NO3 anion acts both as chelating (chelates to the Gd(III) ion) and bridging (between Ni(II) and Gd(III)) ligand and it also links the two symmetrically dependent parts of molecules into one tetranuclear unit through the short bridge between GdIII and GdIII cations. In 1 the ferromagnetic interactions between Ni(II) and Gd(III) (J Ni–Gd  = 0.6(2) cm− 1) as well as Gd(III) and Gd(III) (J Gd–Gd  = 0.5(1) cm− 1) ions are observed.A nitrato-bridged tetranuclear complex [Ni2Gd2(L)2(CH3COO)2(NO3)2](NO3)2·6H2O·4MeOH (1) was synthesized. The magnetic interactions between Ni(II) and Gd(III) as well as Gd(III) and Gd(III) metal centers are ferromagnetic (J Ni–Gd  = 0.6(2) cm− 1 and J Gd–Gd  = 0.5(1) cm− 1).Display Omitted
Keywords: 3d–4f complex; Schiff base; Nitrate coordination modes; Magnetic properties;

Three new lanthanide (III) coordination polymers based on 2-(pyridine-3-yl)-1H-4, 5-imidazoledicarboxylic acid (H3PyIDC) with or without oxalate (Ox) coligand, namely, {[Sm(μ 3-HPyIDC)(H2O)3]·Cl·H2O} n (1), {[Tb(μ 1-H2PyIDC)(μ 2-Ox)(H2O)3]·H2O} n (2), and {[Sm(μ 4-HPyIDC)(μ 2-Ox)0.5(H2O)]·- 2H2O} n (3), have been successfully synthesized. Compound 1 has a two-dimensional (2D) network structure with (4,4) topology based on binuclear [Sm2(COO)2] as secondary building units (SBUs). Compound 2 possesses a 1D lanthanide-oxalate zigzag chain with μ 1-H2PyIDC ligands hanging on both sides. Compound 3 features an unprecedented uninodal 10-connected 3D open framework with (312·424·58·6) topology based on binuclear [Sm2O2] SUBs. The results revealed that the structural diversity is mainly attributed to the different coordination modes of the H3PyIDC ligand as well as the introduction of Ox2 − auxiliary ligand. Moreover, the thermal stabilities and luminescence properties of the selected complexes were also investigated.Three new lanthanide (III) coordination polymers based on 2-(pyridine-3-yl)-1H-4, 5-imidazoledicarboxylic acid with or without oxalate coligand were constructed and studied.Display Omitted
Keywords: 2-(Pyridine-3-yl)-1H-4, 5-imidazoledicarboxylic acid; Structural diversity; Auxiliary ligand;

Monomeric complexes of Re(CO)3 + ion with tridentate N∩N∩Oligands — Schiff base derivatives of salicylic aldehyde by Marek Grzegorczyk; Andrzej Kapturkiewicz; Fabiola W. Sanjuan-Szklarz; Jacek Nowacki (103-106).
Simple synthetic procedures, reactions of Re(CO)5Cl with potentially tridentate N∩N∩OH ligands (Schiff bases prepared from aliphatic or aromatic amines and salicylic aldehyde) lead to formation of monomeric complexes of fac-Re(CO)3 + ion. Three obtained complexes have been characterized by means of elemental analyses and IR, UV–vis, and EI-MS techniques. Molecular structures of the synthesized species were investigated using X-ray diffraction measurements. Depending on the nature of N∩N∩OH ligand the investigated Schiff bases form with fac-Re(CO)3 + ion bidentate or tridentate chelates with N∩N, N∩O or N∩N∩O coordination types.A simple synthetic procedure (reaction between Re(CO)5Cl and the title N∩N∩OH ligand in boiling toluene) leads to novel monomeric fac-Re(CO)3 + complexes.Display Omitted
Keywords: Rhenium carbonyls; Schiff base complexes; N∩N∩OH ligands; X-ray crystallography; EI-MS, IR and UV-vis spectroscopy;

A novel unexpected 1D coordination polymer Nd(Nphgly)(1,2-BDC)(H2O)·2H2O (1) containing simultaneously N-phthaloylglycine (Nphgly) and benzene-1,2-dicarboxylic acid (1,2-BDC) ligands has been prepared under the solvothermal conditions. In situ solvothermal aminolysis reaction occurred at benzene-1,2-dicarboxylic acid and glycine when they reacted with neodymium salts. Furthermore, the magnetic and luminescent properties of 1 were studied.A novel unexpected 1D coordination polymer containing simultaneously N-phthaloylglycinate and benzene-1,2-dicarboxylic acid ligands has been prepared. In situ solvothermal aminolysis reaction occurred at benzene-1,2-dicarboxylic acid and glycine when they reacted with neodymium salts.Display Omitted
Keywords: N-phthaloylglycine; Neodymium; Solvothermal; Magnetism; Luminescence;

A new organically templated open-framework uranyl ethylenediphosphonate by Wan-Guo Tian; Xiu-Yun Yang; Yun-Hui Li; Xiao-Xiao Liu; Weiting Yang; Tao Tian (110-112).
A new organically templated uranyl ethylenediphosphonate, (UO2)5(L)2(HL)2(H2DABCO)2·2H2O (1) (H4L = ethylenediphosphonic acid, DABCO = 1,4-diazabicyclo[2.2.2]octane), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectroscopy and powder X-ray diffraction studies. The structure of compound 1 has been determined to be three-dimensional, which is constructed solely by UO6 square plane bipyramids and ethylenediphosphonate ligands. This open framework contains channels templated by protonated DABCO cations, which serve both as space fillings and charge compensators.A new organically templated uranyl diphosphonate, (UO2)5(L)2(HL)2(H2DABCO)2·2H2O (1) (H4L = ethane-1,2-diyldiphosphonic acid, DABCO = 1,4-diazabicyclo[2.2.2]octane) is hydrothermally synthesized. Its structure solely contains UO6 tetragonal bipyramids and exhibits a three-dimensional characteristic with channels filled by protonated DABCO molecules.Display Omitted
Keywords: Uranyl; Ethylenediphosphonate; Structure; Organic template;

Dinuclear based polymeric copper(II) complexes derived from a Schiff base ligand: effect of secondary bridging moieties on geometrical orientations and magnetic properties by Susanta Hazra; Anirban Karmakar; M. Fátima C. Guedes da Silva; Ľubor Dlháň; Roman Boča; Armando J.L. Pombeiro (113-117).
[1 + 1] condensation of salicylaldehyde and 2-aminobenzenesulfonic acid led to the formation of the acyclic Schiff base o-[(o-hydroxyphenyl)methylideneamino]benzenesulfonic acid (H2L) which, upon reaction with Cu(II) salts in the presence of triethylamine or 4,4′-bipyridine, formed a 2D polymeric species [Cu2L2]n (1) via sulfonate bridge and a 1D polymeric complex [{Cu2L2(4,4′-bipy)}·DMF]n (2) via 4,4′-bipyridine bridge, respectively. The copper cations sit on O4N basal- or O3N2 facial-edge-sharing inverted square pyramidal environments in 1 or 2, respectively. In spite of their comparable compositions, the relative orientations of the metal polyhedra affect the magnetic properties of these polymers since 1, in contrast to 2, presents a strong exchange interaction of an antiferromagnetic nature.Syntheses, structures and magnetic properties of two diphenoxo bridged dicopper(II) based polymeric compounds [Cu2L2]n (1) and [{Cu2L2(4,4′-bipy)}·DMF]n (2) derived from an acyclic Schiff base compartmental ligand H2L, are presented. In spite of their comparable compositions, they exhibit different bridging geometries and magnetic properties.Display Omitted
Keywords: Crystal structures; Coordination polymers; Phenoxo bridges; Magnetic properties;

Two copper(II) isonicotinate complexes, [Cu(INA)2(H2O)4] (1) and {[Cu(INA-N-H)2(μ2 -H2O)2]·2H2O·2NO3}n (2) were prepared using a one-pot synthesis and characterized by single-crystal X-ray diffraction, spectral and thermal analysis and magnetic susceptibility. Complex 1 provides Cu–N(pyridyl) coordination mode with ionic carboxylate functionality. A novel complex 2 exhibits a chain-like crystal structure in which the [Cu(INA-N-H)]2+ ions are bridged by μ2 -H2O molecules. The structural, spectral and thermal correlations indicate significant influence of ligand coordination mode and non-covalent interactions to mentioned properties. Magnetic susceptibility data were fitted by Curie–Weiss law with Tc  = 0.68 K for complex 1 and Tc  = 9.01 K for complex 2. Magnetic studies show a very weak interaction between copper(II) centers within the network structure in complex 1 and stronger ferromagnetic coupling between Cu ions caused by the presence of intra-chain Cu–O–Cu interaction in complex 2.Two copper(II) complexes containing inonicotinate ligand have been successfully synthesized via one-pot synthesis and fully characterized. Moreover, graphical abstract shows molar susceptibility measurements depending on temperature for both prepared compounds.Display Omitted
Keywords: Copper(II); Isonicotinate; Crystal structure; Thermal analysis; Magnetism;

Five isomorphous lanthanide–organic frameworks based on 3-carboxymethoxy phenyl acrylic acid (H2L), [LnL(HCOO)(H2O)] n (Ln = La(1), Ce(2), Pr(3), Nd(4), Y(5)), have been hydrothermally synthesized. X-ray structural analysis reveals that these complexes are rare organic–inorganic hybrid frameworks with unusual (3, 4, 7)-connected (42.6) (44.62) (49.68.84) topology. Moreover, the magnetic properties of 2 and 3 were also investigated and suggested that the thermal depopulation of the crystal-field energy levels of the multiplet, and the antiferromagnetic interactions between Ln3 + ions.Five isomorphous lanthanide–organic frameworks based on 3-carboxymethoxy phenyl acrylic acid have been hydrothermally synthesized. These complexes with unique (3,4,7)-connected (42.6) (44.62) (49.68.84) topology, present rare organic–inorganic hybrid frameworks. Moreover, the magnetic properties of Ce and Pr complexes were also investigated and discussed in detail.Display Omitted
Keywords: Hydrothermal synthesis; 3-Carboxymethoxy phenyl acrylic acid; Antiferromagnetic interactions; Magnetic properties;

Carboranylamidinates of di- and trivalent iron by Philipp Hillebrand; Cristian G. Hrib; Nicole Harmgarth; Peter G. Jones; Volker Lorenz; Marcel Kühling; Frank T. Edelmann (127-129).
For the first time, carboranylamidinates of a transition metal in two different oxidation states have been prepared. The iron carboranylamidinates [o-C2B10H10C(NH i Pr)(= N i Pr)-κ 2 C,N]2FeIIICl (3) and [o-C2B10H10C(NH i Pr)(= N i Pr)-κ 2 C,N]2FeII (4) were simultaneously formed in low yields upon treatment of anhydrous FeCl3 with 2 equiv. of [o-C2B10H10C(NH i Pr)(= N i Pr)-κ 2 C,N]Li(DME) (2) in THF solution. Both products were structurally characterized by single-crystal X-ray diffraction.For the first time, carboranylamidinates of a transition metal in two different oxidation states have been prepared. The iron carboranylamidinates [o-C2B10H10C(NH i Pr)(= N i Pr)-κ 2 C,N]2FeIIICl (3) and [o-C2B10H10C(NH i Pr)(= N i Pr)-κ 2 C,N]2FeII (4) were isolated in low yields by treatment of anhydrous FeCl3 with 2 equiv. of [o-C2B10H10C(NH i Pr)(= N i Pr)-κ 2 C,N]Li(DME) (2) in THF and structurally characterized by single-crystal X-ray diffraction.Display Omitted
Keywords: Carboranes; Amidinates; Carboranylamidinates; Iron; X-ray structure;

Structures and properties of ion pair charge-transfer salts: [DMBPE]2Ge4S10 (DMBPE = N,N′-dimethyl-1,2-bis(4-pyridinium)-ethylene) by Xiao-Lu Sun; Qin-Yu Zhu; Li-Wen Qian; Lan Yu; Zhi-Gang Ren; Guo-Qing Bian; Jie Dai (130-133).
Crystal structures and properties of two new ion pair charge-transfer (IPCT) compounds, [DMBPE]2Ge4S10·8H2O (1) and [DMBPE]2Ge4S10·5H2O (2), (DMBPE = N,N′-dimethyl-1,2-bis(4-pyridinium)-ethylene) are characterized. The IPCT property was confirmed by their charge-transfer absorption bands. Fluorescence emission for 1 in water was observed, that is affected by the cation–anion interaction. The photocurrent measurement showed that compounds 1 and 2 are also photoelectric responsive materials.Two new ion pair charge-transfer thiogermanates are reported; the fluorescence and photoresponse properties of them are also discussed.Display Omitted
Keywords: Thiogermanate; Ion pair charge-transfer; Crystal structure; Photoresponse;

A novel linear [Mn4N8O2] complex: in-situ synthesis, structure and magnetic property by Hua Yang; Su-Na Wang; Da-Cheng Li; Su-Yuan Zeng; Jian-Min Dou (134-136).
A novel mixed-valent tetranuclear manganese complex, [MnII 2MnIII 2(dophe)2(DMSO)7(H2O)] (H5dophe = di-[5-(2-oxyphenyl)-pyrazole]-3-hydroxamic ether) was prepared and characterized through X-ray crystallography, elemental analysis and IR spectra. The molecule contains a linear [MnII 2MnIII 2N8O2] core with two dinuclear ―N―N― bridged subunits connected by two μ 2-O atoms. Two dophe5 − ligands are located opposite to each other. Magnetic studies indicate the dominance of intramolecular antiferromagnetic interactions.Complex 1 consists of four linear arrangement Mn ion linked by two dophe5 − ligand locating opposite to each other to form a linear [MnII 2MnIII 2N8O2] core. Each ligand shows a μ 4:η 1:η 1:η 1:η 1:η 1:η 1:η 1:η 1 coordination model, and they link four Mn ions to form two periphery six-membered chelating rings and five inner five-membered chelating rings and three paratactic rings with a (4, 2, 4) oxo-manganese–nitrogen linear arrangement.Display Omitted
Keywords: Crystal structure; Mn cluster; Pyrazolate-bridging; Magnetic property;

New class of NCS-free cyclometalated ruthenium(II) complexes with 6-phenylpyridine-2-carboxylate for use as near-infrared sensitizers in dye-sensitized solar cells by Takashi Funaki; Hiromi Otsuka; Nobuko Onozawa-Komatsuzaki; Kazuyuki Kasuga; Kazuhiro Sayama; Hideki Sugihara (137-139).
Three examples, FT102, FT90, and FT117 of a new class of NCS-free cyclometalated ruthenium(II) complexes, Ru(tctpy)(O^N^C) (where O^N^C is a tridentate 6-phenylpyridine-2-carboxylate), were synthesized for use as near-infrared (IR) sensitizers in dye-sensitized solar cells (DSSCs). A tridentate donor ligand, 6-phenylpyridine-2-carboxylate was introduced in order to enhance the light harvesting efficiency in the longer wavelength region for the first time. Modifying the ligand improved the photovoltaic performance, and DSSCs sensitized with FT117 exhibited efficient panchromatic sensitization over the entire visible wavelength, extending into the near-IR region. The highest incident photon-to-current conversion efficiency (68%) was found at 600 nm, and the action spectrum onset was near 920 nm.A new class of thiocyanate-free cyclometalated ruthenium(II) complexes was synthesized as near-IR sensitizers for DSSCs. FT117-based cells show efficient panchromatic sensitization over the entire visible wavelength, extending into the near-IR region.Display Omitted
Keywords: Cyclometalated ruthenium(II) complex; 6-Phenylpyridine-2-carboxylate; Dye-sensitized solar cell; Near-IR sensitizer;

Synthesis, characterization and magnetic behavior of four new Co(II) coordination polymers structurally modulated by substituents by Bing Miao; Chao Wei; Yuan-Yuan Xu; Qin-Bo Tan; Jian-Gong Ma; Peng Cheng (140-144).
Four new coordination polymers [Co(btmtmb)2(SCN)2] (1), [Co(bttmb)2(SCN)2] (2), [Co(btmtmb)2(SeCN)2] (3) and [Co(bttmb)2(SeCN)2] (4), where btmtmb = 1,3-bis-(1,2,4-triazol-1-ylmethyl)-5-methoxy-2,4,6-trimethylbenzene and bttmb = 1,3-bis-(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene, have been synthesized and structurally characterized. The X-ray crystal structures reveal that 1 and 3 are constructed of an infinite 1D chain, 2 and 4 contain a 2D (4,4)-network layer. Magnetic properties of the four complexes are investigated, which show that for all these four complexes the antiferromagnetic interactions occur and strong spin–orbit coupling of Co(II) ions exits as well.Four new Co(II) complexes with substituent-group-dependent 1D and 2D structures, respectively, were obtained based on two rarely reported semirigid ligands, which exhibit antiferromagnetic interactions and strong spin–orbit coupling of Co(II) ions.Display Omitted
Keywords: Co(II) coordination polymers; Magnetic properties; Antiferromagnetic interaction; Structural modulation;

DNA binding behaviors and nuclease activities of novel mixed-ligand ruthenium(II) complexes by Naho Iizuka; Sho-ichi Motoki; Misaki Nakai; Yasuo Nakabayashi (145-148).
Two types of ruthenium(II) complexes cis-[Ru(bpy)2ClL]+ and cis-[Ru(bpy)2L2]2 + (L = 1,6-diaminohexane (1,6-dahx), 1-aminohexane (1-ahx)) were synthesized, and the interactions of these complexes with DNA were investigated. Importantly, cis-[Ru(bpy)2(1,6-dahx)2]2 + possessed hydrogen-bonding to DNA, preferentially binds at adenine and/or thymine residues, and exhibits more efficient nuclease activity.Two types of ruthenium(II) complexes cis-[Ru(bpy)2ClL]+ and cis-[Ru(bpy)2L2]2 + (L = 1,6-diaminohexane (1,6-dahx), 1-aminohexane (1-ahx)) were synthesized, and the interactions of these complexes with DNA were investigated.Display Omitted
Keywords: Mixed-ligand ruthenium(II) complex; Hydrogen-bonding; Noncovalent DNA-binding; DNA sequence-specific recognition; Nuclease activity;

Fabrication and visible-light photochromism of novel hybrid inorganic–organic film based on polyoxometalates and ethyl cellulose by Xiaofei Jing; Donglei Zou; Qingling Meng; Wei Zhang; Fengjun Zhang; Wei Feng; Xiangkui Han (149-154).
Novel phosphomolybdic acid/ethyl cellulose hybrid film (denoted as PMoA/EC) was synthesized by entrapping PMoA particles into an EC matrix. The microstructure, visible-light photochromic behaviors and mechanism were fully investigated. The characterizations revealed that spherical PMoA particles dispersed uniformly in the hybrid film and their Keggin geometry were well preserved. The structure of EC was also maintained in the hybrid film after a composite process. Under visible light irradiation, the colorless transparent PMoA/EC hybrid film turned to blue and exhibited high photochromic responsiveness together with reversible photochromism in the presence of oxygen. The appearance of Mo5 + species in XPS spectra indicated that photo-reduction reaction has occurred between PMoA particles and the EC matrix and suggested proton transfer mechanism during the photochromic process. To the best of our knowledge, EC was used to construct polyoxometalate-based hybrid film with visible light photochromism for the first time.Novel phosphomolybdic acid/ethyl cellulose hybrid film (denoted as PMoA/EC) was successfully synthesized by entrapping PMoA particles into an EC matrix. Remarkably, the resulted hybrid film exhibited high visible light photochromic responsiveness together with reversible photochromism in the presence of oxygen. Meanwhile, the proton transfer mechanism was identified due to the appearance of Mo5 + species during the photochromic process.Display Omitted
Keywords: Polyoxometalates; Ethyl cellulose; Hybrid film; Visible-light photochromism;

Systematic assembly of {LnMnIII 4} appended cubanes with inorganic polyoxometalate ligands and their electrocatalytic property by Yi-Zhen Chen; Zhu-Jun Liu; Zhi-Ming Zhang; Huan-Yu Zhou; Xiao-Tao Zheng; En-Bo Wang (155-158).
Exploration of the reactivity of the versatile polyoxometalate precursor [β2 -SiW11O39]8 − with lanthanide cations, transition-metal cations, carbonate, and morpholine, afforded a group of new appended cubanes {LnMnIII 4} (Ln = HoIII, TmIII, YbIII, SmIII, GdIII, ErIII and CeIV). The appended cubanes {LnMnIII 4} were encapsulated by two inorganic polyoxometalate ligands, resulting in a series of heterometallic cluster-based sandwich-type compounds: K10Na3[{LnIIIMnIII 4(μ3 -O)2(μ 2-OH)2(H2O)(CO3)}(β-SiW8O31)2]·xH2O (Ln = HoIII, x = 24 for 1; Ln = TmIII, x = 22 for 2; Ln = YbIII, x = 21 for 3); K7Na6[{LnIIIMnIII4(μ3 -O)2(μ 2-OH)2(H2O)(CO3)}(β-SiW8O31)2]·xH2O (Ln = SmIII, x = 22 for 4; Ln = GdIII, x = 20 for 5; Ln = ErIII, x = 22 for 6) and K7Na5[{CeIVMnIII 4(μ 3-O)2(μ 2-OH)2(H2O)(CO3)}(β-SiW8O31)2]·24H2O (7), which were characterized by single-crystal X-ray diffraction analyses, IR spectroscopy, and thermal gravimetric analysis. Electrocatalytic study reveals that these compounds exhibited the activity of electrocatalytic reduction of sodium nitrite.A series of Ln cations were introduced into the reaction system of [β2 -SiW11O39]8 -, transition metal ions, organic ligand and CO3 2 − resulting in a group of {LnMnIII 4} cubanes stabilized by inorganic polyoxometalate ligands.Display Omitted
Keywords: Lacunary polyoxometalate; Heterometal; Cubane; Systematic synthesis;

Nickel(II) thiolates derived from transmetallation reaction of [Zn(Tab)4](PF6)2 with Ni(II) ions and their catalytic activity toward the C―N coupling reactions by Jing Shi; Fu-Ling Li; Hong-Xi Li; Fan Wang; Hong Yu; Zhi-Gang Ren; Wen-Hua Zhang; Jian-Ping Lang (159-162).
Reactions of NiCl2·6H2O or Ni(ClO4)2·6H2O with 2,2′-bipyridine (2,2′-bipy), or 2-bis(diphenylphosphino)ethane (dppe) or 1,4-bis(diphenylphosphino)butane (dppb) followed by addition of [Zn(Tab)4](PF6)2 (1) resulted in the formation of one trinuclear cationic complex [(2,2′-bipy)4Ni3(μ-Tab)4]Cl0.5(PF6)5.5 (2), one mononuclear cationic complex [Ni(Tab)2(dppe)](PF6)2 (3), and one dinuclear cationic complex [Ni2(dppb)(μ-Tab)2(Tab)2](PF6)2(ClO4)2 (4). Complexes 24 were characterized by elemental analysis, IR, UV–vis, 1H and 31P NMR, and single-crystal X-ray diffraction. In the [(2,2′-bipy)4Ni3(μ-Tab)4]6 + hexacation of 2, the central Ni(II) atom is connected to two [Ni(2,2′-bipy)2]2 + fragments by two pairs of μ-Tab ligands, forming a linear trinuclear cationic structure. The Ni(II) center of the dication of 3 is tetrahedrally coordinated by two S atoms from two Tab ligands and two P atoms of one dppe ligand. Complex 4 has a dimeric cationic structure in which two [(Tab)Ni]2 + species are linked by a pair of μ-Tab ligands and one dppb ligand. Complexes 24 displayed high catalytic activity toward the cross-coupling reactions of arylboronic acids and amines to produce N-arylated amines.Reactions of [Zn(Tab)4](PF6)2 with Ni(II) ions and 2,2′-bipy, dppe or dppb produced one trinuclear cationic complex, one mononuclear cationic complex and one dinuclear cationic complex. These three complexes displayed high catalytic activity toward the cross-coupling reactions of arylboronic acids with amines to produce N-arylated amines.Display Omitted
Keywords: Nickel(II) thiolate complex; 4-(Trimethylammonio)benzenethiolate; Transmetallation; Crystal structure; Catalysis;

Two kinds of 3D coordination frameworks from monometallic to 4d–4f heterometallic: Synthesis, crystal structures, photoluminescence and magnetic properties by Xing-Rui Ran; Ning Wang; Wen-Jing Liu; Wei-Ping Xie; Jin-Ying Gao; Chu-Jun Chen; Yi Long; Shan-Tang Yue; Ying-Liang Liu; Yue-Peng Cai (163-171).
Two kinds of three-dimensional (3D) coordination frameworks from monometallic to heterometallic, including a charming 3D monometallic complex, namely, [Eu2(mpda)3(H2O)4]n (1) and the first series of novel 3D heterometallic 4d–4f coordination frameworks based on 2,6-dimethylpyridine-3,5-dicarboxylic acid, namely, [Ln2Cd2(mpda)2(bdc)2(SO4)2(H2O)6]n [Ln = Sm(2), Eu(3), Gd(4), Tb(5), Dy(6); mpda = 2,6-dimethylpyridine-3,5-dicarboxylic acid; bdc = 1,4-benzenedicarboxylic acid] have been successfully synthesized under hydrothermal conditions and structurally characterized. Crystal 1 is featured by its interesting 3D chain-layer construction which is formed by the alternative arrangement of chains and layers and exhibits 2-nodal 5, 6-connected 3D network with the Schlafli symbol of {33.43.55.64}{36.46.53}. Complexes 2–6 are isostructural and it reveals that these 3D heterometallic compounds are firstly built by H2mpda ligand. What is worth mentioning is that anionic ligand SO4 2 − plays a crucial function in the construction building. The two-dimensional (2D) lanthanide-transition heterometallic bilayers [Ln2Cd2(mpda)2(bdc)2]n are pillared by SO4 2 − subunits forming mixed-ligand complexes with a pillared-layer 3D structure. Complexes 2–6 feature 4-nodal 3, 4, 5, 6-connected 3D frameworks with {4.82}{4.84.10}{42.810.102.12}{42.88} topology. All the complexes are characterized by elemental analyses, FT-IR spectroscopy, Powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Furthermore, the luminescence properties of compounds 1, 3, and 5 and the magnetic properties of complexes 4 and 6 were also investigated in detail.Two kinds of 3D coordination frameworks, containing an interesting 3D monometallic complex and the first series examples of Ln(III)–Cd(II) 4d–4f 3D heterometallic compounds, have been successfully synthesized under hydrothermal conditions based on 2,6-dimethylpyridine-3,5-dicarboxylic acid.Display Omitted
Keywords: Heterometallic compounds; Anionic ligand; Pillared-layer; Luminescence; Magnetic;

A series of unusual three-dimensional 3d–4f (Ln/Cu/Cl/Br) cyanide heterometallic coordination polymers: Synthesis, crystal structure and magnetic properties by Ying-Zhao Ma; Ruo-Ting Dong; Chu-Wen Li; Mo-Yuan Shen; Chong-Jian Zhao; Cheng-Feng Yang; Hong Deng (172-175).
A series of unusual three-dimensional (3D) 3d–4f cyanide heterometallic coordination polymers (HCPs), namely [Ln1.5Cu3(ina)3(ga)(CN)1.5(X)(H2O)] [Ln = Dy, X = Cl (1), Ln = Tb, X = Br (2), Ln = Dy, X = Br (3); ina = isonicotinic acid; ga = glycolic acid] have been synthesized via hydrothermal reaction and characterized by single crystal X-ray diffraction, elemental analyses, FT–IR spectroscopy, powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). X-ray structural analysis reveals that HCPs 1 to 3 are constructed from the linkage between Ln–organic layer motifs and double-stranded cyano-containing Cu-inorganic ribbon motifs. In these complexes, the carboxyl group and hydroxyl group of H2ga are all deprotonated and the coordinated ga ligands adopt a very interesting μ 3-kO:kO,O′:kO′,O″ coordination mode. Moreover, magnetic properties of HCP 1 were investigated.The linkage between Dy-organic layer motifs and double-stranded cyano-containing Cu-inorganic ribbon motifs gives the 3-dimensional heterometallic coordination polymers.Display Omitted
Keywords: 3d–4f Coordination polymers; Copper–cyanide system; Glycolic acid; Magnetism;

Three platinum(II) complexes, including 2-(2-methoxy-phenyl) imidazo [4,5-f]-[1,10] phenanthroline, 2-(3-methoxy-phenyl) imidazo [4,5-f]-[1,10] phenanthroline and 2-(4-methoxy-phenyl) imidazo [4,5-f]-[1,10] phenanthroline, were synthesised and structurally characterised. In complexes 13, the platinum centre adopts a four-coordinate square planar geometry. In the MTT assay, these complexes exhibited considerable cytotoxicities against the SPC-A-2, MGC80-3, BEL-7404 and HeLa human tumour cell lines, with IC50 values in the range of 4.7 ± 0.8 to 23.3 ± 0.4 μM, and lower cytotoxicities towards the HL-7702 human normal liver cell line. By flow cytometry analyses, the HeLa cells treated with complexes 13 for 72 h exhibited DNA damage at the sub-G1 phase with a dose-dependent effect resulting in the blockage of cell cycle at sub-G1 phase, which might contribute to the cell apoptosis observed in HeLa cells. From the results of the CD, UV–vis and FID spectral analyses, complexes 13 showed good binding affinity with human telomeric G-quadruplex DNA. It suggested the potential inhibition on the telomerase activity, which should be a key antitumour mechanism for complexes 13. Furthermore, complex 1 with 2-substituted MOIP ligand, which may have lower steric hindrance for DNA intercalation, showed higher G-quadruplex DNA binding affinity than complexes 2 and 3. This was supported by the results from cell growth inhibition and cell apoptosis induction.Three platinum(II) complexes 13 bearing with 2-(methoxy-phenyl)imidazo[4,5-f]-[1,10] phenanthroline ligands showed higher cytotoxicities against SPC-A-2, MGC80-3, BEL-7404 and HeLa human tumour cell lines with IC50 values in the range of 4.7–23.3 μM than the HL-7702 normal liver cell line. They significantly induced cell apoptosis and blocked the cell cycle at sub-G1 phase in HeLa cells, in which the 2-methoxy substituted ligand showed the better cell apoptosis induction. Complexes 13 also suggested potent inhibitions on telomerase activity due to their higher binding affinities with human telomeric G-quadruplex DNA than with double helix DNA.Display Omitted
Keywords: 2-(Methoxy-phenyl) imidazo [4,5-f]-[1,10] phenanthroline; Platinum(II) complex; Cytotoxicity; Cell apoptosis; G-quadruplex;

The compound [Zn2(flmq)2(bdc)(H2O)2], 1, based on flumequine (Hflmq) and 1,4-benzenedicarboxylate (bdc), has been synthesised and shown by single crystal X-ray analysis to contain one-dimensional chains linked into sheets by hydrogen bonding. Photoluminescent measurements on the complex in the solid state show that it displays strong photoluminescence at 467 nm.[Zn2(flmq)2(bdc)(H2O)2], based on flumequine (Hflmq) and 1,4-benzenedicarboxylate (bdc), has been synthesised and shown to contain one-dimensional chains linked into sheets by hydrogen bonding. The compound displays strong photoluminescence at 467 nm.Display Omitted
Keywords: Flumequine; Coordination polymer; Zinc; Crystal structure; Luminescent;

One novel metallacrown: [Na6Co6(EDBA)6(CH3CH2OH)(CH3CH2O)2][CoCl4]2 (1, EDBA = 2,2′-(((ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(oxy))dibenzoic anion), has been synthesized under hydrothermal condition. Compound 1 crystallizes in the cubic system with space group Pa-3, and displays a structure with a [24-MCNa-6] periphery encapsulating the [12-MCCo-6] inner core. Magnetic investigations suggest that weak ferromagnetic coupling exists between adjacent Co2 + in 1.A novel metallacrown [Na6Co6(EDBA)6(CH3CH2OH)(CH3CH2O)2][CoCl4]2 (1, EDBA = 2,2′-(((ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(oxy)dibenzoic anion) was synthesized and structurally characterized. Magnetic investigations suggest that weak ferromagnetic coupling exists between adjacent Co2 + centers.Display Omitted
Keywords: 2,2′-(((ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(oxy)dibenzoic anion); Metallacrown; Cobalt; Ferromagnetic coupling;

An unprecedented zigzag-shaped heptanuclear ferric cluster: synthesis, structure and magnetism by Pei-Pei Yang; Wei-Wei Kuang; Yun Xu; Shao-Min Li; Tao Han (187-190).
The synthesis, crystal structure and magnetochemical characterization are reported for a new FeIII 7 cluster, [FeIII 7(L)4(O2CPh)8(H2O)2]NO3·3CH3CN (1). Complex 1 was synthesized from the use of the potentially O,N,O,O tetradentate chelate, 3-(2-hydroxybenzylideneamino)propane-1,2-diol (H3L), in the presence of carboxylate groups. Inspection of the central core reveals that it contains two triangular subunits sharing a common vertex Fe2, and then the vertex Fe3 (Fe3A) is further bonded to Fe4 (Fe4A) by a μ2 -Oalkoxide atom from the L3 − ligand, generating the unprecedented zigzag arrangement heptanuclear Fe7 unit. Variable temperature magnetic susceptibility studies for 1 reveal the presence of only antiferromagnetic exchange interactions. Complex 1 shows no evidence of slow relaxation behavior above 2.0 K.A novel heptanuclear ferric complex, containing an unprecedented zigzag arrangement Fe7 unit, has been obtained. Magnetic behavior indicates that only antiferromagnetic exchange interactions are present in the Fe7 cluster.Display Omitted
Keywords: Heptanuclear ferric cluster; Crystal structure; Zigzag shape; Magnetic properties;

One rutile Co(II) coordinated polymer with bifunctional ligand by Ling Qin; Yuan-Yuan Wang; Jian-Liang Zhou; He-Gen Zheng (191-193).
One new 2-fold interpenetrating three-dimensional (3D) compound with rutile {4·62}2{42·610·83} topology, [Co2(L)2]·DMF·6H2O (1) (H2L = 4,4′-((4-(pyridin-4-yl)phenyl)azanediyl)dibenzoic acid, DMF = N,N-dimethylformamide) has been synthesized under hydrothermal condition. The compound 1 was characterized by IR spectra, thermal analysis and single crystal X-ray diffraction. In addition, UV–Visible spectra of compound 1 are also depicted.One new 2-fold interpenetrated three-dimensional compound [Co2(L)2]·DMF·6H2O with a pyridine-carboxylate bifunctional ligand has been synthesized. The compound contains rutile {4·62}2{42·610·83} topology.Display Omitted
Keywords: Bifunctional ligand; Crystal structure; Rutile topology; Coordination polymer;

Syntheses, structures and properties of silver(I) complexes constructed from nitrogenous aromatic heterocyclic carboxylic acids and N-donor ligands by Hong-Ling Gao; Qin-Qin Zhang; Chi Wai Cheung; Yong-Ling Yi; Fang-Fang Li; Jing Qu; Shu-Xin Jiang; Xue-Ying Shi; Jian-Zhong Cui (194-197).
Four new coordination complexes with silver(I) ions and nitrogenous aromatic heterocyclic carboxylic ligands, namely [Ag4(pztc)(phen)4] · 8H2O (1), {[Ag4(pztc)(bpe)3] · 5H2O}n (2), [Ag4(Hmptc)2(4,4′-bpy)3] · 4.5H2O (3), and [Ag2(H2mptc)2(2,2′-bpy)2] (4) (H4pztc = pyrazine-2,3,5,6-tetracarboxylic acid, H3mptc = 6-methyl-2,3,5-pyridine-tricarboxylic acid, phen = 1,10-phenanthroline, bpe = trans-1,2-bis(4-pyridyl)ethylene, 4,4′-bpy = 4,4′-bipyridine, 2,2′-bpy = 2,2′-bipyridine), have been synthesized by the self-assembly reactions and characterized by X-ray diffraction single crystal structure analysis, elemental analysis, IR, PXRD, fluorescence and thermal analysis. In 1, four crystallographically independent silver(I) atoms are found to coordinate with only one pztc4 − ligand. Complex 2 is a 2D grid structure. Complexes 3 and 4 are extended from 0D to 2D or 1D by the Ag⋯O interactions.Four Ag-containing complexes constructed from mixed ligand of pyrazine-2,3,5,6-tetracarboxylic acid (H4pztc) or 6-methyl-2,3,5-pyridinetricarboxylic acid (H3mptc) and N-donor ligands are designed and synthesized. Notably, H2O/ethanol/acetonitrile conditions have been the preferred method employed by our group to enhance the solubility of the silver carboxylates, which provide a new way of Ag complex synthesis.Display Omitted
Keywords: Silver(I) complexes; Nitrogenous aromatic heterocyclic carboxylic acids; N-donor ligands; Ag⋯O interactions;

The oxidation of alcohols to corresponding aldehydes and ketones has been achieved using polymetallic complexes as catalyst with hydrogen peroxide as the terminal oxidant under a solvent free condition. These polymetallic complexes linked to a single ligand system exhibited remarkable cooperative effect in the oxidation process. This ecologically friendly procedure releases water as the only by-product.Synergy between copper and zinc centers in the complexes has provided a greener route in efficient oxidation of alcohols to the corresponding carbonyl compounds using H2O2 as an oxidant.Display Omitted
Keywords: Cooperative catalysis; Polymetallic complexes; Oxidation; Alcohols; Carbonyl compounds;

Synthesis, crystal structures and cytotoxic activity of mononuclear nickel(II) and dinuclear zinc(II) complexes with ligand derived from S-benzyldithiocarbazate by Xiao-Yang Qiu; Chi Zhang; Su-Zhi Li; Guang-Xiu Cao; Peng Qu; Fu-Qiang Zhang; Jian-Gong Ma; Bin Zhai (202-206).
Ni(L)2 (1) and Zn2(μ-OL)2(L)2 (2), (HL = S-benzyl-β-N-(2-bromobenzylidene) dithiocarbazate), were synthesized and characterized by elemental analysis and X-ray single-crystal diffraction analysis. 1 is a mononuclear neutral nickel(II) complex and the center nickel atom is chelated by donors of N2S2 possessing a distorted tetrahedral configuration, while in 2, the adjacent two complex molecules are linked through two O atoms to form a dimer and the center zinc atom is five-coordinate in a distorted trigonal–bipyramidal geometry. The cytotoxic activity study indicated that 2 showed potent cytotoxic activity against the human liver hepatocellular carcinoma (HepG2) cancer cell lines, with IC50 2.4 ± 0.2 μg·mL− 1, which is slightly weaker than 5-fluoroacil (5-FU) (0.89 ± 0.21 μg·mL− 1) as reference. A gel electrophoresis assay demonstrated the ability of the complex to cleave the pBR322 plasmid DNA.The flexible thiosemicarbazone ligand has two coordination modes in complexes 1 and 2. The cytotoxic activity study indicated that complex 2 showed potent cytotoxic activity against the human liver hepatocellular carcinoma and gastric carcinoma cancer cell lines.Display Omitted
Keywords: Nickel(II) and zinc(II) complexes; Crystal structure; Cytotoxic activity; DNA cleavage;

Ionothermal synthesis, crystal structures and magnetic properties of two nickel(II) coordination polymers based on tetrazole-1-acetic acid by Jun Chen; Shuai-Hua Wang; Zhi-Fa Liu; Mei-Feng Wu; Yu Xiao; Rong Li; Fa-Kun Zheng; Guo-Cong Guo (207-211).
Ionothermal reaction of NiCl2·6H2O and tetrazole-1-acetic acid (1-Htza) in ionic liquid [BMIM]Br (BMIM = 1-butyl-3-methylimidazolium) afforded a new 3D Ni(II) coordination polymer [Ni(1-tza)2]n 1. When 2,2′-bipy was introduced, another 1D chained polymer, [Ni(1-tza)(2,2′-bipy)(H2O)2]nXn·2nH2O (2, X = 0.78Br + 0.22Cl) was acquired. Both compounds have been structurally characterized by single-crystal X-ray diffraction analyses. In the obtained compounds, 1-Htza ligands adopt two different coordination modes: μ 3-κN4:κO1:κO2 for 1, and μ 2-κN4:κO1 for 2. The temperature-dependent magnetic susceptibilities of 1 and 2 have been measured and theoretically fitted by means of a 1-D chain model. A ferromagnetic interaction between Ni(II) ions exists in 1 with J  = 3.24 cm− 1, while an antiferromagnetic interaction in 2 with J  = − 5.72 cm− 1.Two nickel(II) coordination polymers have been synthesized from ionothermal reactions, which represents new examples of using ionic liquids as solvents in synthesizing tetrazolate–carboxylate complexes. Compound 1 possesses a 3-D structure with a (426288101)(4261)2 topology. When bidentate chelating 2,2′-bipy was introduced, 1-D zigzag chained 2 was generated.Display Omitted
Keywords: Ionothermal synthesis; Nickel(II) coordination polymer; Tetrazole-1-acetic acid; Magnetic properties; Crystal structure;

A luminescent cyclic binuclear zinc–pamoate complex for highly selective and sensitive sensing of 2,4,6-trinitrophenol by Limei Zhao; Junwei Ye; Wenbing Li; Raji Feyisa Bogale; Bin Wang; Weitao Gong; Guiling Ning (212-215).
A luminescent cyclic binuclear zinc–pamoate complex, [Zn2(PAM)2(1,3-PDA)2] (1), has been synthesized by self-assembly of Zn(II) ions, 4,4′-methylenebis(3-hydroxy-2-naphthalenecarboxylic acid) (H2PAM) and 1,3-propanediamine (1,3-PDA) under hydrothermal condition and characterized by elemental analysis, infrared spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction analysis. In 1, two Zn2 + ions are bridged by two PAM ligands to form a 24-membered ring binuclear structure. The emission of 1 could be quenched efficiently and selectively by 2,4,6-trinitrophenol(TNP), indicating that 1 can serve as a selective chemosensor for the detection of TNP via a fluorescence quenching mechanism.A luminescent cyclic binuclear zinc–pamoate complex, [Zn2(PAM)2(1,3-PDA)2] (1), has been synthesized and can serve as a selective chemosensor for the detection of TNP via a fluorescence quenching mechanism.Display Omitted
Keywords: Cyclic binuclear complex; Zinc–pamoate; Luminescent; 2,4,6-Trinitrophenol; Chemosensor;

A solvothermal and mechanochemical strategy for the construction of chiral N,N-ditopic metalloligands: oxygenation process of a Cu(I)X/quinine system by Daniel Prochowicz; Iwona Justyniak; Arkadiusz Kornowicz; Szymon Komorski; Janusz Lewiński (216-218).
Oxygenation process of a CuX/QN system (where X = Cl, Br; QN―H = quinine) involving either a solvothermal or mechanochemical approach affords novel chiral N,N-ditopic metalloligands [XCu(μ-QN)]2. The molecular and crystal structures of the resulting complexes have been determined by single-crystal X-ray diffraction and PXRD.The novel chiral N,N-ditopic metalloligands by oxygenation process of CuX/QN systems under both solvothermal and liquid-assisted grinding conditions have been synthesized and characterized.Display Omitted
Keywords: Mechanochemistry; Metalloligand; Copper; Oxygenation; Cinchona alkaloid;

Four photoluminescent homochiral supramolecular compounds based on enantiopure 2-(1-hydroxy-ethyl)-3H-benzoimidazole-5-carboxylate ligand have been synthesized successfully, and all of them are built from fascinating butterfly-like chains via hydrogen bonding interactions.Four photoluminescent homochiral supramolecular compounds based on enantiopure 2-(1-hydroxy-ethyl)-3H-benzoimidazole-5-carboxylate ligand have been synthesized successfully, and all of them are built from fascinating butterfly-like chains via hydrogen bonding interactions.Display Omitted
Keywords: Homochiral; Photoluminescence; Supramolecular compounds; Coordination polymers;

Synthesis of alkoxy derivatives of the 10-vertex manganadecaborane [nido-6-Mn(CO)3B9H13][NMe4] by Pei Ma; Tiffany M. Smith; Jon Zubieta; James T. Spencer (223-225).
The facile synthesis of cyclic oxonium derivatives of the manganadecaborane 1 is reported. A reported THF substituted compound 2 was prepared by using this method. The yield was improved to 90% from previously reported 26%. A similar 1,4-dioxane substituted compound was also prepared and its structure was confirmed by single crystal X-ray diffraction studies. This demonstrates the success of the approach and extends the cyclic oxonium methods to metallaboranes.The alkoxy derivatives of a manganadecaborane [nido-6-Mn(CO)3B9H13][NMe4] can be easily prepared using our method. The yield was improved to 90% from previously reported 26% for one derivative. This method will be useful for fictionalization of metallaborane complex.Display Omitted
Keywords: Metallaborane; Polyhedral borane; Alkoxy derivatives;

A dual functional porous NbO-type metal–organic framework decorated with acylamide groups for selective sorption and catalysis by Rui-Rui Cheng; Song-Xue Shao; Hai-Hong Wu; Yan-Fei Niu; Jie Han; Xiao-Li Zhao (226-228).
A dual functional three-dimensional porous NbO-type metal–organic framework with inserted acylamide units was solvothermally synthesized, which exhibits large CO2-uptake capacity (160 cm3  g− 1 at 1 bar), high selectivity toward CO2/N2 (41.6 at 273 K) and satisfied catalytic activity in Knoevenagel condensation reaction.A dual functional three-dimensional porous NbO-type metal–organic framework with inserted acylamide units exhibits large CO2-uptake capacity, high selectivity toward CO2/N2 and satisfied catalytic activity in Knoevenagel condensation reaction.Display Omitted
Keywords: Metal–organic framework; Acylamide; CO2-uptake; Knoevenagel condensation;

Synthesis and characterization of new biologically active palladium(II) complexes with (1E,6E)-1,7-bis(3,4-diethoxyphenyl)-1,6-heptadiene-3,5-dione by Natalia Miklášová; Eva Fischer-Fodor; Roman Mikláš; Lenka Kucková; Jozef Kožíšek; Tibor Liptaj; Olga Soritau; Jindra Valentová; Ferdinand Devínsky (229-233).
Two new palladium complexes with (1E,6E)-1,7-bis(3,4-diethoxyphenyl)-1,6-heptadiene-3,5-dione, 1 and 2, have been synthesized and structurally characterized. Complex 1 has the molecular structure confirmed by X-ray diffraction measurements. Both complexes display a significant antiproliferative activity against human colorectal cancer cells by inducing early and late apoptotic processes in those cells.Palladium(II) complexes with curcumin analogues capable to trigger early and late apoptosis in human colorectal cancer cells.Display Omitted
Keywords: Palladium(II) complexes; Curcuminoid; Antiproliferative activity; Cytotoxicity; Apoptosis; Colorectal cancer;

Synthesis and structural characterization of new cyclopalladated compounds containing hybrid pyrazole ligands by Miguel Guerrero; José Antonio Perez; Josep Ros; Josefina Pons (234-236).
Two new cyclopalladated complexes with 2-(5-methyl-3-phenyl-1H-pyrazol-1-yl)ethanol (HL1) ligand: [PdCl(L1)(HL1)] (1) and [Pd(NO3)(L1)(HL1)] (2) were prepared and fully characterized by elemental analyses, conductivity measurements, mass spectrometry, IR and NMR spectroscopies. In complexes 1 and 2, one of the ligands is bidentately coordinated to the Pd atom through the N pz atom and the C ph atom (L1), and the other ligand only presents monodentately coordination to the N pz atom (HL1). The metallic atom completes the coordination with a Cl (1) or NO3 (2) anion in monodentate form, respectively. This synthetic approach represents an easy and convenient method for the design of attractive cyclopalladated complexes.The synthesis of two new Pd(II) cyclopalladated complexes with 2-(5-methyl-3-phenyl-1H-pyrazol-1-yl)ethanol is described. For the synthesis of these complexes, we have developed a simple one-pot and general method and we have proven the different coordination modes of HL1 (monodentate and bidentate). The method here described is a simple pathway to obtain cyclopalladated compounds in mild conditions and represents an easy and convenient method for the future design of potential cyclopalladated catalysts.Display Omitted
Keywords: Cyclopalladated; N-Hydroxyalkylphenylpyrazole; Pyrazole ligand; Palladium(II) complexes;

A novel colorimetric chemosensor for multiple target ions in aqueous solution: simultaneous detection of Mn(II) and Fe(II) by Kyung Beom Kim; Gyeong Jin Park; Hyun Kim; Eun Joo Song; Jeong Mi Bae; Cheal Kim (237-240).
We have synthesized a new Schiff base 1 having julolidine moiety, which detects Mn2 + and Fe2 + through naked eye in aqueous solution. The sensor 1 exhibited significant color changes from pale yellow to orange for Mn2 + and to dark green for Fe2 +. The complex formations were proposed to be 1:1 ratio, based on Job plot and ESI-mass spectrometry analysis. The detection limits of Mn2 + and Fe2 + were found to be 7.11 μM and 0.14 μM, respectively, which are below the WHO acceptable limits (manganese: 7.28 μM and iron: 5.36 μM) in drinking water.We have synthesized a new Schiff base 1 having julolidine moiety, which detects Mn2 + and Fe2 + through naked eye in aqueous solution. The sensor 1 exhibited significant color changes from pale yellow to orange for Mn2 + and to dark green for Fe2 +. The complex formations were proposed to be 1:1 ratio, based on Job plot and ESI-mass spectrometry analysis.Display Omitted
Keywords: Colorimetric; Chemosensor; Schiff base; Manganese; Iron;

Mixed-valent diruthenium diphosphonate containing zigzag chain structure of {Ru2(hedp)2(SCN)} n 4n by Dan Wang; Huai-Qing Yang; Guang-Hao Wu; Xiao-Feng Hou; Jian-Hui Yang; Bin Liu (241-243).
This paper reports the crystal structure and magnetism properties of a novel mixed-valent diruthenium(II,III) complex, [C(NH2)3]4[Ru2(hedp)2(SCN)]·4H2O (1), where hedp represents 1-hydroxyethylidenediphosphonate. It shows a zigzag chain structure in which the paddlewheel diruthenium(II,III) dimers of Ru2(hedp)2 3 − linked by SCN bridges. The chains are stacked along the [011] direction with strong intra- and interchain hydrogen bonds. Magnetic studies show that significant antiferromagnetic exchanges are mediated between the [Ru2(hedp)2]3 − (S  = 3/2) units through thiocyanate ion bridges. Structural analysis proves that the Ru―Ru bond weakening ability is H2O < Br  < Cl  < μ-NCS  < μ-NC  < μ-SCN.High stable lantern-type geometry unit Ru2(hedp)2 3 − linked by SCN forms zigzag chain structure {Ru2(hedp)2(SCN)} n 4n. Antiferromagnetic exchanges are mediated between the Ru2 units through SCN bridges, and the Ru―Ru bond weakening ability is H2O < Br  < Cl  < μ-NCS  < μ-NC  < μ-SCN.Display Omitted
Keywords: Diruthenium; Diphosphonates; Thiocyanate; Structure; Magnetism;

An unprecedented seven-connected coordination network based on octanuclear supertetrahedral lead(II) cluster as a secondary building unit by Shaomin Cheng; Baoxia Dong; Xiangfei Wang; Fang Yang; Meng Tang; Hang Chen; Limin Yuan; Wenlong Liu (244-247).
A novel two-dimensional (2D) lead(II) coordination polymer, {[(Me2NH2)4[Pb8(μ 4-O)(1,2,3-btc)6]]2·6DMF·2H2O}n (1) (1,2,3-H3btc = benzene-1,2,3-tricarboxylic acid; DMF = N,N-dimethylformamide; Me2NH2 +  = the countercationic dimethylammonium ion, generated in situ via the hydrolysis of the solvent DMF), was synthesized solvothermally and fully characterized by single crystal X-ray diffraction, thermogravimetry and solid-state luminescence analysis. Structural analysis reveals that complex 1 contains an unusual octanuclear tetrahedron @ tetrahedron lead(II) secondary building units (SBUs) [Pb8(μ 4-O)(O2C)18] and is extended topologically into a rare uninodal 7-connected framework structure. At room temperature, 1 in the solid-state exhibits strong emission peak at 495 nm originated from ligand to metal charge transfer (LMCT) between delocalized π bonds of carboxylate groups and p orbitals of lead(II) centers.Reaction of Pb(NO3)2 with benzene-1,2,3-tricarboxylic acid yields an unprecedented seven-connected coordination bilayer anion network with octanuclear supertetrahedral lead(II) clusters as SBUs.Display Omitted
Keywords: Lead(II) coordination polymer; Octanuclear lead(II) secondary building unit; 7-Connected net; Photoluminescence;

A versatile metal-organic framework for carbon dioxide capture and modulating fluorescence properties of Alq3 by Ya-Juan Xiao; Chun-Yi Sun; Guo-Chun Yang; Liang Zhao; Zhong-Min Su (248-250).
A versatile three-dimensional four-fold interpenetrated metal-organic framework [Zn5(btz)6(bdc)2(H2O)2]·7DMA (1) has been synthesized under solvothermal condition, which has two types of channels running along a and b axes with dimension of approximately 7.5 × 9 Å2 and 8.5 × 11 Å2. With the appropriate and permanent porosity, compound 1 exhibits high adsorption of CO2 and good capability to encapsulate Alq3 (tris(8-hydro-xyquinoline)aluminum) chromophores to realize tunable fluorescence at solid state. To the best of our knowledge, this material is a rare example of MOFs that exhibit good capability to tune luminescence properties of Alq3.A three-dimensional fourfold interpenetrated MOF exhibits high adsorption of CO2 and good capability to encapsulate Alq3 chromophores to realize tunable fluorescence.Display Omitted
Keywords: Metal-organic framework; Gas sorption; Encapsulation of Alq3; Tunable luminescence;

A new Co2 +-centered heteropolyoxomolybdate nanocluster containing the bipy ligand (4,4′-bipy = 4,4′-bipyridine), with formula [4,4′-H2bipy][Co0.23Mo6O20]·2H2O (1), has been hydrothermally synthesized and structurally characterized by means of FT-IR, atomic absorption spectroscopy, single-crystal and powder X-ray diffraction (XRD). The catalytic investigations disclosed that 1 displayed both good activity and stability in the epoxidation of cyclooctene. It can also be recovered easily and reused in the reaction without significant loss of activity or selectivity. Furthermore, the effect of the type of oxidant and solvent on the conversion of the reaction was investigated.A new Co2 +-centered polyoxomolybdate hybrid material was hydrothermally synthesized under controlled pH value and structurally characterized. The prepared inorganic–organic hybrid has been found to be a selective and active heterogeneous catalyst for the epoxidation of cyclooctene.Display Omitted
Keywords: Nanocluster; Inorganic–organic hybrid; Heteropolyoxomolybdate; Cyclooctene epoxidation;

The crystallization of [CuCl2(L1)] (L1  = bis-[(1-pyrazolyl)methyl]ethylamine) by ethanol/hexane solvent diffusion afforded the compound [CuCl2(L2)]2 (L2  = 1-[2-(ethylamino)methyl]pyrazole), which has been characterized by single-crystal X-ray diffraction, elemental analysis, conductivity measurements, infrared and UV–vis spectroscopies. There are very few polynuclear complexes with N-alkylaminopyrazole ligands reported so far. Especially L2 ligand, which is forming the binuclear copper(II) complex has been obtained for the first time here. The crystal structure consists of a dimeric unit in which the copper(II) atoms are five-coordinated in a distorted square pyramidal geometry with two nitrogen and two chlorine atoms in the base and one chlorine in the apical vertex. At the supramolecular level attractive structural designs are obtained, particularly, a peculiar Ferris wheel-like shape along the (110) direction. Hydrogen bonds constitute the main pillars of the supramolecular self-assembly observed.Ferris wheel-like shape at the supramolecular self-assembly of the [CuCl2(1-[2-(ethylamino)methyl]pyrazole)]2 complex.Display Omitted
Keywords: Binuclear copper(II) complex; N-alkylaminopyrazole; Supramolecular array;

A co-ligand firstly introduced to 9-fluorenone-2,7-dicarboxylate-based MOF: synthesis, structure and photoluminescent property by Yi-Qiang Mu; Min-Le Han; Bing-Hai Wang; Wei Xia; Wen-Wen Dong; Dong-Sheng Li (259-262).
Through hydrothermal reactions, 4,4′-bipyridine (bpy) co-ligands firstly was introduce to CdII–H2FDC system (H2FDC = 9-fluorenone-2,7-dicarboxylic acid), generating a new coordination polymer {[Cd2(FDC)2(bpy)]∙H2O} n (1). Compound 1 has a pillar-layer 2-fold interpenetrating pcu network, based on the square-grid tetranuclear [Cd4(COO)8] units. Interestingly, 1 shows a blue-shifted photoemission, as well as enhanced fluorescence lifetime compared with the pure H2FDC ligand.A 3D Cd metal–organic framework based on 9-fluorenone-2,7-dicarboxylate and 4,4′-bipyridine is presented, which possesses a pillar-layer 3D pcu 2-fold interpenetrating network, constructed from the distorted square-grid tetranuclear [Cd4(COO)8] units and shows interesting emission properties.Display Omitted
Keywords: CdII-MOFs; 9-Fluorenone-2,7-dicarboxylate; Crystal structure; Luminescence property;

Appraisal of DNA obligatory, DNA cleavage and in vitro anti-biogram efficiency of 9,10-phenanthrenequinone based metal complexes by Natarajan Raman; Thesingu Rajan Arun; Rajkumar Mahalakshmi; Seemon Packianathan; Rajendran Antony (263-267).
This work presents the synthesis and characterization of four new metal(II) complexes of 9,10-phenanthrenequinone based Schiff base precursor. From UV–vis, FT-IR, 1H NMR, EPR and Raman spectral data, an octahedral geometry has been assigned to the complexes. The molar conductivity and magnetic moment measurements indicate the non-electrolytic and monomeric nature of the complexes. DNA binding ability of these complexes has been explored using diverse techniques viz UV–vis absorption, cyclic voltammetry, fluorescence spectroscopy and viscometry. Comparative DNA oxidative cleavage ability of the complexes has been accomplished under UV photo radiation on pBR322 DNA. These studies reveal that they are good metallointercalators and chemical nucleases. In addition, the biocidal action of the complexes is investigated against few pathogenic bacteria and fungi by well diffusion method. The screening data reveal that the complexes exhibit more efficient antimicrobial activity than the free ligand. These findings may lead to develop novel metal based drugs.The synthesized 9,10-phenanthrenequinone based complexes have good in vitro DNA binding and cleavage efficacy. They are efficient antimicrobial and metallointercalators. These findings may lead to develop novel DNA targeting metallonucleases.Display Omitted
Keywords: Schiff base; Metal complexes; Metallointercalators; DNA cleavage; Methionine;

Synthesis, luminescence and gas absorption of a new polythreading coordination polymer by Lu Lu; Xi-Ren Wu; Jian-Qiang Liu; Jia-Min Wu; Qin-Lin Li; Jian-Hui Man; Yi Hu; Mei-Shan Li; Jun Wang; Ming Lin; Olivier Guillou; Ng Seik Weng (268-272).
A new compound of {[Zn(btb)(Hbib)]·2H2O·CH3OH}n (H3btb = 1,3,5-benzenetrisbenzoate and bib = 1,4-bis(2-methyl-imidazol-1-yl)butane) was synthesized and characterized. The coordination polymer shows a new (2D → 3D) polythreaded array that is obtained from the self-assembly of adjacent 2D layers with dangling lateral arms, in which each large hexagonal void of one layer is threaded by two dangling lateral arms of two adjacent layers belonging to two identical spatial orientations. The luminescence study indicates that the title compound emits bright red fluorescence compared to the free ligand at room temperature. In addition, the small-sized and non-polar pores do not enable 1 to attract CO2 and N2 strongly, which can be confirmed by the computational method based on Connolly's algorithm.A new coordination network shows 2D → 3D feature. The gas absorption behavior of 1 has been explored by the computational method based on Connolly's algorithm and experimental confirmation.Display Omitted
Keywords: Luminescence; Topology; Gas absorption;

Luminescent platinum(II) chloride complexes of 6-(1-alkyl-5-tetrazolyl)-4,4′-dimethyl-2,2′-bipyridine terdentate chelating ligands by Jing-Lin Chen; Xiu-Zhen Tan; Xing-Feng Fu; Zong-Hao Guo; Jin-Yun Wang; Hua-Guang Yu; Li-Hua He; He-Rui Wen (273-276).
Two new luminescent platinum(II) chloride complexes with N-alkylated 6-(1H-5-tetrazolyl)-4,4′-dimethyl-2,2′-bipyridine (tmbpyH), [Pt(etmbpy)Cl](BF4) (1) and [Pt(htmbpy)Cl](BF4) (2) (etmbpy = 6-(1-ethyl-5-tetrazolyl)-4,4′-dimethyl-2,2′-bipyridine; htmbpy = 6-(1-hexyl-5-tetrazolyl)-4,4′-dimethyl-2,2′-bipyridine), have been prepared and characterized. Complex 1 adopts a distorted square-planar geometry and exhibits a dimeric assembly with a head-to-tail fashion and weak Pt⋯Pt interaction. A moderately intensive broad absorption band is displayed at 350–465 nm in CH3CN solution for 1 and 2, perhaps originating from the metal-to-ligand charge-transfer (MLCT) states mixed with some halide-to-ligand charge-transfer (XLCT) and intra-ligand (IL) ππ* characters, as supported by their TD-DFT calculations. Complexes 1 and 2 show the photoluminescent properties in PMMA films and solid state at ambient temperature, which are influenced by the alkylation of the tetrazolyl-NH of tmbpyH.Two new luminescent Pt(II) chloride complexes with the N-alkylated 6-(1H-5-tetrazolyl)-4,4′-dimethyl-2,2′-bipyridine (tmbpyH) have been synthesized and characterized. It is demonstrated that the N-alkylation of the tetrazolyl ring has a significant effect on the solubilities and luminescence properties of the tmbpyH-based Pt(II) complexes.Display Omitted
Keywords: Platinum(II) complexes; Crystal structure; Photoluminescence; 6-(1-Alkyl-5-tetrazolyl)-4,4′-dimethyl-2,2′-bipyridine;

Investigation of SO2 gas adsorption in metal–organic frameworks by molecular simulation by Xue-Dan Song; Se Wang; Ce Hao; Jie-Shan Qiu (277-281).
Sulfur dioxide (SO2) is responsible for the formation of acid rain and many other undesirable environmental and health hazards. Therefore, the capture or separation of sulfur dioxide is an important gas treatment process in industry. In this study, we predicted the adsorption of SO2 in ten metal–organic frameworks (MOFs), and investigated the effects of heat of adsorption, free volume, and surface area on sulfur dioxide uptake using grand canonical Monte Carlo simulations over a wide range of pressures. The molecular simulations of the SO2 adsorption isotherms in the MOF materials revealed that having high SO2 adsorption capacity and a suitable pore size greater than 0.4 nm is essential. In this pore size range, at low pressures the amount of SO2 adsorbed in these MOF materials is correlated with the heat of adsorption. Furthermore, at moderate pressures the amount of SO2 adsorbed is not well-correlated with the free volume and the accessible surface area, but the free volume and surface area are still clearly important characteristics in evaluating any potential SO2 absorption and storage absorbent. In addition, it was found that MOFs show higher SO2 storage capacity than most hydrotalcite-like materials at low pressure. This result suggests that MOF materials have potential as sulfur-transfer catalysts in industry.We investigated the effects of heat of adsorption, free volume and surface area on adsorption of SO2 in the MOFs using MC simulations. It demonstrates that some of the MOFs show higher SO2 storage capacity than most hydrotalcite-like materials. These MOFs as sulfur-transfer catalysts are expected to be applied in industry.Display Omitted
Keywords: Metal–organic frameworks; SO2 gas; Gas adsorption; Molecular simulation;

Two isomorphous compounds [Eu(2,2′-bpdc)(NO3)(e-urea)3]n (1) and [Tb(2,2′-bpdc)(NO3)(e-urea)3]n (2) (2,2′-bpdc2 −  = 2,2′-biphenyldicarboxylate and e-urea = ethyleneurea) have been synthesized using a deep-eutectic solvent of choline chloride/e-urea. The lanthanide ions are linked by the 2,2′-bpdc2 − ligands to form one-dimensional helical chains in these compounds. Of special interest is the presence of parallel left- and right-handed single helices with the ratio of 1:1 in both compounds. Detailed photoluminescence studies show that both compounds exhibit typical lanthanide luminescent emissions and the excitation energy has been efficiently transferred to the lanthanide ions from the organic ligands.Two lanthanide coordination polymers with helical chain structures were synthesized ionothermally from a deep-eutectic solvent of choline chloride/e-urea. Both compounds exhibit typical lanthanide luminescent emissions. The efficient transfer of the excitation energy from organic ligands to the Ln3 + ions was observed.Display Omitted
Keywords: Ionothermal synthesis; Helical chain; Luminescence; Deep-eutectic solvent;

Entangled coordination polymers have attracted considerable interest due to their novel structures and potential applications. In this paper, one new 2D → 3D porous zinc coordination polymer {[Zn2(DPDBT)2(OBA)2](H2O)3} n (1) with parallel polycatenation was synthesized under solvothermal conditions based on 2,8-di(pyridin-4-yl)dibenzo[b,d]thiophene (DPDBT) ligand. In addition, complex 1 exhibits interesting solid-state photoluminescence and high thermal stability.A 2D → 3D porous zinc coordination polymer, exhibiting interesting solid-state photoluminescence and high thermal stability, was synthesized based on 2,8-di(pyridin-4-yl)dibenzo[b,d]thiophene (DPDBT) ligand.Display Omitted
Keywords: Self-assembly; Pyridyl ligands; Luminescence; Thermal stability;

0D and 1D PbII complexes constructed from pyridyldicarboxamide by varying the ratios of mixed solvent by Xiangyu Zhang; Yuhong Zhang; Shuzi Liu; Hong Xu; Jinpeng Li; Hongwei Hou (289-294).
By varying the ratio of mixed reaction solvent, the reactions of PbAc2 with N,N′-bis(1,3,4-thiobiazolyl)-2,6-pyridyldicarboxamide (H2btapca) afford two different crystal structures: a novel discrete hexanuclear cage of formula [Pb6(btapca)6]·(H2O)2 (1) and a 1-D double-chain polymer [Pb2(btapca)2(H2O)2]n (2). Fluorescence investigations reveal that both complexes display enhanced emissions in contrast to the free ligand H2btapca.A discrete hexanuclear cage of [Pb6(btapca)6]·(H2O)2 and a 1-D double-chain polymer [Pb2(btapca)2(H2O)2]n have been assembled by the reactions of PbAc2 with N,N′-bis(1,3,4-thiobiazolyl)-2,6-pyridyldicarboxamide (H2btapca) under different mixed reaction solvents. Both complexes have enhanced fluorescence in contrast to the free ligand.Display Omitted
Keywords: Crystal structure; Lead ion; Pyridyldicarboxamide; Solvent influence; Fluorescence;

Facile in situ syntheses of new templates and formations of three zinc phosphates by Guo-Ming Wang; Jin-Hua Li; Xiao Zhang; Ji-Qing Jiao; Zhen-Zhen Bao; Xiao-Meng Zhao; Wen-Wen Jiang; Ying-Xia Wang; Jian-Hua Lin (295-300).
Three new organically templated zinc phosphates, namely, [dmdabco][Zn2(HPO4)3]·(H2O) (1), [tmpip]0.5[Zn2(HPO4)2(H2PO4)] (2) and [tmpip][Zn3(HPO4)4] (3) (dmdabco  = N,N′-dimethyl-1,4-diazabicyclo[2,2,2]octane, tmpip  = N,N,N′,N′-tetramethyl-piperazinium), were successfully synthesized under solvothermal reactions and structurally characterized by single-crystal X-ray diffraction. The dmdabco 2 + and tmpip 2 + templating agents were derived respectively from simple in situ N-alkylation transformations between the methanol solvent and organic cyclic aliphatic diamines, 1,4-diazabicyclo[2,2,2]octane (dabco) in 1 and 1-methylpiperazine in 2 and 3. Such direct methylation feature is unique, and quite different from conventional Eschweiler–Clarke methylation in which an excess of formic acid and formaldehyde was required. Compound 1 exhibits a 4-connected 2D (4, 4) net with pentameric [Zn2(HPO4)3] clusters as secondary building units (SBUs); 2 possesses a complex double layered structure with 12-ring windows. Compound 3 has a (3, 4)-connected 3D pcu architecture with heptameric [Zn3(HPO4)4] clusters as SBUs, forming intersecting 8- and 12-ring channels.Three new zinc phosphates have been prepared with templates generated by hydrothermal in situ N-methylation transformations between amine precursors and methanol solvent.Display Omitted
Keywords: Zinc phosphate; Crystal structure; N-alkylation; In situ; Solvothermal synthesis;

The adsorption aspect of Cu2 + and Zn2 + on MCM-41 and SDS-modified MCM-41 by Suwimol Wongsakulphasatch; Worapon Kiatkittipong; Janekit Saiswat; Bovornlak Oonkhanond; Alberto Striolo; Suttichai Assabumrungrat (301-304).
To determine the interaction mechanism for heavy metal adsorption on functionalized MCM-41 mesoporous silica, both macroscopic and microscopic investigation was performed in this study. Hybrid sorbent material has been developed by modifying MCM-41 with sodiumdodecylsulphate (SDS), named as SDS-MCM-41, and tested for capturing Cu2 + and Zn2 + in the solution. Zeta potentials of pristine MCM-41, SDS-MCM-41, and the adsorbents that adsorbed Cu2 + and Zn2 + for different pHs and initial metal ion concentrations were employed to estimate macroscopically the adsorption ability. Molecular dynamics (MD) simulation were performed to investigate adsorption behavior in microscopic point of view. Zeta potential and molecular simulation reveal that SDS functional groups are responsible for the adsorption of metal ions through the interaction between the anionic charged surface of SDS-MCM-41 and the cationic metal ions. The qualitatively consistent results of molecular dynamics simulations with experiments suggest the possibility of applying computer simulation for preliminarily selection of adsorbent functional groups for removal of Cu2 + and Zn2 +.SDS-modified MCM-41.Display Omitted
Keywords: Modified-functionalized mesoporous material; Copper; Zinc; Metal ions removal; Chelating agent;

Two novel Pb(II) complexes, [Pb(HL1)(2,2′-bpy)(MeOH)]n, (HL1 = 2-hydroxyl-5-methyl-1,3-disulfonate dianion) (1) and [Pb1.5(OH)(L2)]n, (L2 = 2-hydroxyl-5-nitro-benzenesulfonate dianion) (2), involving ortho-hydroxyl arenesulfonic acids, have been synthesized and characterized for the first time. Complex 1 exhibits helical chain motif with hemidirected Pb(II) spheres, while complex 2 presents layer motif with rarely mixed hemidirected and holodirected Pb(II) spheres. Considering the secondary Pb―O bonds, the two complexes are extended to layer and 3-D pillared layered framework with holodirected Pb(II) spheres.Two new Pb(II)–sulfonate complexes have been obtained, which exhibit structure extension through the modulation of Pb(II) geometry from hemidirected to holodirected tuned by secondary Pb―O bonds.Display Omitted
Keywords: Lead(II) complex; Hemi- and holodirected geometries; Arenesulfonates; Crystal structure;

A rhodamine-based fluorescent chemosensor was synthesized and characterized, which demonstrated excellent specificity toward Pd2 +. Upon addition of Pd2 +, the ring-opening process of rhodamine spirolactam resulted in remarkably enhanced fluorescent accompanied by distinct color changes. Commonly coexistent metal ions displayed little interference to the sensor. Obviously, these unique results suggested that the chemosensor could serve as a potential naked-eye sensor for Pd2 +. The detection limit was 0.19 μM. In addition, we prepared the test strips of sensor for Pd2 + detection, which provided a simple and convenient method for determination of Pd2 + in palladium-containing water samples. Importantly, the sensor was successfully used for fluorescence imaging in HepG2 cells.A novel chemosensor for the visual detection of Pd2 + imaging in living cells.Display Omitted
Keywords: Pd2 +; Chemosensor; Naked-eye; Test strips; Bioimaging;

The reactions of 2-(((2-hydroxy-3-methoxyphenyl)methylene)amino)-2-(hydroxymethyl)-1,3-propanediol (H4L) and Mn(ClO4)2·6H2O or Co(SCN)2·3H2O in the presence of triethylamine in methanol led to the formation of two new complexes [MnΙΙΙ 4(HL)2(H2L)2(CH3OH)4]·4CH3OH·(ClO4)2 (1) and [CoΙΙCoΙΙΙ(H2L)2(CH3OH)(SCN)]·1.5CH3OH·1.5H2O (2), respectively. According to structural data and magnetic properties tetranuclear complex 1 contains four homo-valence manganese (ΙΙΙ) atoms, while in the binuclear complex 2 composed of hetero-valence bi- and trivalent cobalt (ΙΙ, ΙΙΙ) atoms. Weak antiferromagnetic exchange interactions between neighboring manganese ions in 1 have place. χMT for 2 was fitted using a model of isolated cobalt (ΙΙ) ion with zero-field splitting parameters and the study confirms its mixed valence CoΙΙ/CoΙΙΙ nature. No slow magnetic relaxation effects were observed for both complexes in the absence of an applied dc magnetic field.Homo-valence tetranuclear manganese and hetero-valence binuclear cobalt complexes with the formula [MnΙΙΙ 4(HL)2(H2L)2(CH3OH)4]·4CH3OH·(ClO4)2 (1) and [CoΙΙCoΙΙΙ(H2L)2(CH3OH)(SCN)]·1.5CH3OH·1.5H2O (2) have been structurally and magnetically characterized.Display Omitted
Keywords: Polydentate Schiff base ligand; Manganese; Cobalt; Structural characterization; Magnetic property;

Exploring the coordination chemistry of 2-picolinic acid to zinc and application of the complexes in catalytic oxidation chemistry by Stephan Enthaler; Xiao-Feng Wu; Maik Weidauer; Elisabeth Irran; Peter Döhlert (320-323).
Oxidation reactions are one of the fundamental processes in organic chemistry and in recent years the application of low-toxic and abundant catalysts became a significant research target. In this regard, the application of zinc catalysis has been established. For instance the in situ mixture of zinc(II) bromide and pyridines substituted with carboxylic acid functions has been demonstrated to oxidize e.g. alcohols to aldehydes with hydrogen peroxide as terminal oxidant. However, no information on the structural composition of the in situ systems has been accounted so far. In this study we tried to shed light on these in situ systems and report on the synthesis, isolation and characterization of zinc(II) complexes modified with 2-picolinic acid (2). In more detail, [Zn(2-H)(2)Br] and [Zn(2-H)2(H2O)2] were obtained and subsequently tested in catalytic oxidation reactions. Both complexes showed catalytic activity in the oxidation of benzyl alcohol to benzaldehyde. Importantly, a lower activity was observed compared to the in situ system. Several experiments were performed to understand the different reactivity and it was found that a significant effect on oxidation processes revealed by the HBr, which is produced as side product in the in situ complex formation.Zinc complexes modified with 2-picolinic acid have been synthesized, characterized and applied in oxidation catalysis.Display Omitted
Keywords: Zinc complexes; Bidentate ligand; Catalysis; Oxidation chemistry;

Two interpenetrating networks based on 1,4-bis(2-methylimidazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (bmimx), namely, {[Zn2(bmimx)2(cba)2]·2.5H2O}n (1) and {[Zn(bmimx)(suc)]·2H2O}n (2) (H2cba = 4,4′-carbonyldibenzoic acid, H2suc = succinic acid) have been prepared at hydrothermal condition by varying the dicarboxylate ligands. Single-crystal X-ray diffraction indicates that complex 1 shows a 4-connected dmp net with 3-fold interpenetration which contains 1D (Zn − cba)n right- and left-handed helical chains; complex 2 shows a dia topology with 4-fold interpenetration. The results indicate that the spacers of dicarboxylate coligands have an important effect on the interpenetrating characters and ultimate frameworks. Moreover, the photoluminescence properties of the two complexes were studied in the solid state at room temperature.Two different Zn(II) interpenetrating networks have been synthesized by varying the dicarboxylate ligands. Complex 1 shows a dmp net with 3-fold interpenetration; complex 2 exhibits a dia topology with 4-fold interpenetration. The structural differences indicate that the spacers of dicarboxylate coligands have an important effect on the interpenetrating characters and ultimate frameworks.Display Omitted
Keywords: Dicarboxylate acids; Flexible imidazole-based ligand; Photoluminescent properties; Interpenetrating networks;

Synthesis and characterization of three novel 3D metal–organic frameworks constructed from semi-rigid V-shaped ligands by Zhao Jin; Huanyu Zhao; Xiaojun Zhao; Xiangdong Yao; Guangshan Zhu (329-334).
Three new 3D metal-organic frameworks (MOFs) [Ni3(L1)2(4,4′-bipy)4(H2O)6]∙6H2O (1), [Ni(HL2)(4,4′-bipy)(H2O)3]∙(4,4′-bipy) (H2O) (2) and [Mn3(L2)2(H2O)(DMF)2] (3) based on the semi-rigid V-shaped ligands, 4-(4-carboxyphenoxy) phthalic acid (H3L1) and 3-(4-carboxyphenoxy)phthalic acid (H3L2), have been successfully synthesized under the hydrothermal and solvothermal condition, and characterized by elemental analysis, thermal studies, and powder and single-crystal X-ray diffraction. The results indicate that in compound 1, the H3L1 ligands adopt bis-monodentate coordination mode to connect the two kinds of 1D ―Ni-4,4′-bipy-Ni― chains, giving a 3D network with rare (42·63·8)2(6·84·10) topological structure. In compound 2, H3L2 ligand acts as the terminal mode while the 4,4′-bipy ligands bridge the Ni(II) ions to generate infinite ―Ni-4,4′-bipy-Ni― zig-zag chains, which furthermore through intermolecular O―H⋯O, O―H⋯N hydrogen bonds form a three-dimensional (3D) supramolecular structure. While in compound 3, H3L2 ligand exhibits u6—η1: η1: η2: η1: η1: η2 coordination mode to bridge six Mn (II) ions, leading to a 3D open framework. Further photoluminescence measurement indicates that compound 1 could be a potential candidate as photoactive material.Three new MOFs, [Ni3(L1)2(4,4′-bipy)4(H2O)6]∙6H2O (1), [Ni(HL2)(4,4′-bipy)(H2O)3]∙(4,4′-bipy) (H2O) (2) and [Mn3(L2)2(H2O)(DMF)2] (3), have been obtained under hydrothermal and solvothermal conditions. Single-crystal X-ray diffraction reveals that the formed structural architectures are strongly dependent on the configuration and coordination models of the V-shaped semi-rigid ligands. Furthermore, photoluminescence experimental results suggest compound 1 as a potential purple-emitted photoactive material.Display Omitted
Keywords: 3D open metal–organic framework; Semi-rigid V-shaped ligand; (42·63·8)2(6·84·10) topological structure; Photoactive materials;

Synthesis and crystal structure of the bi-metallic hybrid compound {Mn4(2,2′-bipyridine)2Sb4S10} by Carolin Anderer; Christian Näther; Wolfgang Bensch (335-339).
The new bi-metallic inorganic–organic hybrid compound {Mn4(2,2′-bipyridine)2Sb4S10} was synthesized under solvothermal conditions. Its 2D-layered network contains distinct heterocubanes constructed by SbS3 pyramids, MnS6 and MnN2S4 octahedra. The interconnection of these units leads to a layered structure with ellipsoidal rings with pores of dimension 7.8 Å · 8.8 Å.The layers composed of {Mn4(2,2′-bipyridine)2Sb4S10} are arranged in such way that the bipy-ligands are interlocked.Display Omitted
Keywords: Solvothermal synthesis; Hybrid compounds; Thioantimonate; Crystal structure;

The hydrothermal reaction of Ln(NO3)3·6H2O, 3-(4-carboxyphenyl)-2,6-pyridinedicarboxylic acid (H3cppdc) and N,N-dimethylformamide (DMF) gave a series of lanthanide coordination polymers n[NH2(CH3)2]·[Ln(cppc)2(H2O)2] n (where: Ln = Ce (1), Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), Tb (7), Dy (8), Ho (9) and Er (10); and H2cppc = 5-(4-carboxyphenyl)-2-pyridinecarboxylic acid). The H2cppc ligand was formed in situ via decarboxylation of the initial H3cppdc ligand under the hydrothermal reaction conditions. Complexes 110 that crystallized in the same C 2/c space group, exhibited similar 2D layered structures and assemble into 3D supramolecular networks via hydrogen bonding and π–π stacking interactions. In addition, the luminescence properties of complexes 4, 5, 7 and 8 were investigated.Display Omitted
Keywords: Hydrothermal synthesis; Crystal structure; Decarboxylation; Luminescence;