Inorganic Chemistry Communications (v.14, #8)

Contents List (iii-x).

by Tom Clark (1191).

Study of the first antibacterial agent pipemidic acid modifying Keggin polyoxometalate by Chunjiang Li; Jingmei Lu; Fan Tu; Jingying Chen; Yujia Li (1192-1195).
A new compound based on polyoxometalates (POMs) and the quinolone antibacterial pipemidic acid (HPPA), {[Co(PPA)2]H2[ SiW12O40]}·HPPA·3H2O (1), has been prepared and characterized by elemental analyses, IR and singe crystal X-ray diffraction. The title compound represents the first example of POMs modified by the quinolone antibacterial HPPA, in which the POMs are modified by [Co(HPPA)2] subunits. Its antitumor activity on MCF-7 cells was investigated by the. The results show that the title compound exhibits higher antitumor activity than its parent, which indicates that introduction of M-PPA into the POM surface can increase their antitumor activity and make the compounds to penetrate into the cells easily.The first compound based on POMs and the quinolone antibacterial pipemidic acid was prepared. And the results of antitumor activity indicate that introduction of M-PPA into the polyoxoanion surface can increase their antitumor activity and make the compounds to penetrate into the cells easily.Display Omitted
Keywords: Keggin polyoxometalate; Pipemidic acid; Antitumor activity; MCF-7;

Synthesis, characterization, and catalytic activities of rare-earth metal complexes with iminopyrrolyl ligands by Shuangliu Zhou; Chengwei Yin; Hui Wang; Xiancui Zhu; Gaosheng Yang; Shaowu Wang (1196-1200).
A series of rare-earth metal complexes with substituted iminopyrrolyl ligands were prepared and characterized. Reactions of [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 with 3 equiv. of 2-(2,6-Et2C6H3N═CH)C4H3NH (1a) in toluene generated tris-iminopyrrolyl rare-earth metal complexes with formula [2-(2,6-Et2C6H3N═CH)C4H3N]3Ln(THF)n [n = 0, Ln = Y (2a), Eu (2b); n = 1, Ln = Nd (2c), Sm (2d)] in moderate yields. Treatments of [(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 with 3 equiv. of 2-(2,4,6-Me3C6H2N═CH)C4H3NH (1b) in toluene afforded tris-iminopyrrolyl rare-earth metal complexes with formula [2-(2,4,6-Me3C6H2N═CH)C4H3N]3Ln(THF) [Ln = Y (3a), Sm (3b), Eu (3c)]. The catalytic properties of all rare-earth metal complexes on the ring-opening polymerization of ε-caprolactone have been studied. The results represent rare example of the pyrrolyl ligands as initiators for ε-caprolactone polymerization.A series of rare-earth metal complexes with tris-iminopyrroly ligands were synthesized and characterized. The complexes exhibited high catalytic activities towards ring-opening polymerization of ε-caprolactone.Display Omitted► Iminopyrrolyl rare-earth metal complexes were prepared. ► Complexes showed good catalytic activities on the ε-caprolactone polymerization. ► Pyrrolyl ligands as initiators for ε-caprolactone polymerization.
Keywords: Rare-earths; Catalyst; Iminopyrrolyl; Ring-opening polymerization; ε-Caprolactone;

A new three-dimensional coordination polymer with the formula, [Cd4(OH)2(na)6] n (1) (na = nicotinate), has been hydrothermally synthesized and structurally characterized, which can be considered as a uninodal six-connected pcu topology based on butterfly-like [Cd43-OH)2] SBUs. The polymer exhibits high thermal stability until 355 °C confirmed by thermogravimetric analysis and has potential applications as an optical material.A new three-dimensional coordination polymer has been hydrothermally synthesized and structurally characterized, which can be considered as a uninodal six-connected pcu topology based on butterfly-like [Cd43-OH)2] SBUs. The polymer exhibits high thermal stability until 355 °C as confirmed by thermogravimetric analysis and may have potential applications as an optical material.Display Omitted► A new three-dimensional coordination polymer were hydrothermally synthesized. ► It can be considered as a uninodal six-connected pcu topology. ► It exhibits high thermal stability and purple photoluminescence emission.
Keywords: [Cd43-OH)2]; Pcu topology; Cd(II) complex; Luminescence;

Temperature-controlled dimensionality variety from 3D to 2D and 1D based on Cd(II)/ip/bmb polymers by Chunying Xu; Linke Li; Qianqian Guo; Hongwei Hou; Yaoting Fan (1204-1208).
By controlling the hydrothermal reaction temperature, three coordination polymers with the same ingredients but different dimensional architectures from 3D to 2D and 1D have been obtained, namely, [Cd(bmb)(Hip)2] n (1), {[Cd(bmb)(ip)]·H2O} n (2), and [Cd(bmb)(ip)(CH3CH2OH)(H2O)] n (3) (bmb = (1,4-bis(2-methylbenzimidazol-1-ylmethyl) benzene); H2ip = 1,3-benzenedicarboxylic acid). A careful investigation of the structures discloses that temperature parameters have significant effects on the conformations and coordination modes of the ligands and enhanced temperature favors the formation of higher dimensional products. In addition, the thermal stabilities and photoluminescence properties of polymers 13 in the solid state have also been investigated.The dimensionality of Cd(II)/ip/bmb polymers have been adjusted from 3D self-penetrated pillared-layer framework to 2D grid-layer and 1D trapezoid-like chain by varying the hydrothermal reaction temperature. In addition, these polymers show high thermal stability and different fluorescent emissions.Display Omitted► Three coordination polymers with the same ingredients but different dimensional architectures from 3D to 2D and 1D. ► Temperature parameters have significant effects on the conformations and coordination modes of the ligands. ► Enhanced temperature favors the formation of higher dimensional products.
Keywords: Temperature; Dimensionality; Cadmium; Photoluminescence;

Hydrothermal synthesis, crystal structure and property of a barbell-like copper complex with {(μ-F)[(μ-O)2(NbF4)2]} as the handle bar by Kundawlet Alimaje; Mingguan Liu; Jun Peng; Pengpeng Zhang; Xiang Wang; Min Zhu; Dandan Wang; Cuili Meng (1209-1211).
A new Cu-Nb mixed complex, [{Cu2(phen)4(μ-O)2(NbF4)2}(μ-F)][NbF6] (1) (phen = 1,10-phenanthroline), was hydrothermally synthesized, and characterized by elemental analyses, IR spectra, thermogravimetric analysis and single crystal X-ray diffraction. Compound 1 exhibits a discrete barbell-like copper cluster with {(μ-F)[(μ-O)2(NbF4)2]} fragment as the handle bar, and [NbF6] is a counter-anion. Fluorescent property, solubility, and electrochemical property of compound 1 were studied.A new Cu and Nb mixed complex which exhibits a discrete barbell-like copper cluster with {(μ-F)[(μ-O)2(NbF4)2]} fragment as the handle bar was hydrothermally synthesized.Display Omitted► A new Cu and Nb mixed complex was hydrothermally synthesized. ► The complex exhibits a discrete barbell-like tetrametallic cluster. ► The complex has strong fluorescence.
Keywords: Barbell-like; Hydrothermal synthesis; Fluorescence spectrum; Electrochemical property;

Reactions of the phosphinic amide ligand N-(4-methyl-2-pyrimidinyl)-P,P-diphenyl-phosphinic amide, L, with the corresponding metal salts afforded the complexes [Zn(L)Cl2], 1, and Co3(L)4Br6, 2, which have been structurally characterized by X-ray crystallography. The molecules of the free L ligands are interlinked through N–H―N and C–H―O hydrogen bonds to form a linear chain, whereas complex 1 shows the 1D helical chain structure, which is the first coordination polymer containing phosphinic amide ligands, and 2 is a linear Co(II) trimer with a rare mixed T dO hT d geometry. While the free L ligand adopts the aligned conformation, those in 1 and 2 adopts the cis and both the cis and trans conformations, respectively.Two new complexes, [Zn(L)Cl2], 1, and Co3(L)4Br6, 2, containing the phosphinic amide ligand N-(4-methyl-2-pyrimidinyl)-P,P-diphenyl-phosphinic amide, L, are reported. The molecules of the free L ligands are interlinked through N–H―N and C–H―O hydrogen bonds to form a linear chain, whereas complex 1 shows the 1D helical chain structure, which is the first coordination polymer containing phosphinic amide ligands, and 2 is a linear Co(II) trimer with a rare mixed Td–Oh–Td geometry. While the free L ligand adopts the aligned conformation, those in 1 and 2 adopts the cis and both the cis and trans conformations, respectively.Display Omitted► We report two new complexes, [Zn(L)Cl2], 1, and Co3(L)4Br6, 2, containing the phosphinic amide ligand N-(4-methyl-2-pyrimidinyl)-P,P-diphenyl-phosphinic amide. ► Complex 1 shows the 1D helical chain structure, which is the first coordination polymer containing phosphinic amide ligands. ► Complex 2 is a linear Co(II) trimer with a rare mixed T dO hT d geometry.
Keywords: Zinc; Cobalt; Phosphinic amide; 1-D coordination polymer;

Three novel group IIB metal complexes [Zn3(L 4 )2Cl6] n (1), {[Cd(L 4 )Cl2](H2O)} n (2) and [Hg(L 4 )Cl2]2 (3) with a multidentate N-donor building block 3,4-bis(2-pyridyl)-5-(3-pyridyl)-1,2,4-triazole (L 4 ) have been prepared and characterized. Single crystal X-ray diffraction analysis reveals that 1 is a 2D layered coordination polymer constructed from the linkage of [Zn3(μ-Cl)2] trinuclear units by L 4 spacers, 2 shows a 1D coordination pattern with [Cd2(μ-Cl)2] dinuclear units and L 4 spacers in pair, whereas 3 has a discrete dinuclear structure. The metal ions used in the assembled processes will dominate the final coordination motifs of these complexes, as also, their extended supramolecular architectures in virtue of various secondary interactions. The solid state properties such as thermal stability and fluorescence of 13 are also found to be closely related to the metal centers.Three supramolecular complexes with the group IIB metals and a novel tripyridyltriazole tecton have been synthesized, which exhibit diverse 2D, 1D and dimeric coordination motifs regulated by the metal centers. Their thermal and fluorescent properties have also been discussed.Display Omitted► Three group IIB metal complexes with a novel tripyridyltriazole ligand are obtained. ► Their distinct supramolecular lattices are dominated by the nature of metal centers. ► These complexes show different thermal and fluorescent behaviors.
Keywords: Group IIB metal complexes; Tripyridyltriazole ligands; Metal-regulated assemblies; Crystal structures; Solid state properties;

Photoluminescent improvement of SrMoO4 by the electrochemical formation of Ca2+-doped solid solutions by Yong Sun; Junfeng Ma; Jingrui Fang; Chang Gao; Zhensen Liu (1221-1223).
Pure SrMoO4 and CaMoO4, and SrMoO4 solid solution crystallites were successfully prepared by a simple electrochemical process. The photoluminescence (PL) of SrMoO4 can be greatly improved by incorporating Ca2+ into its matrix to form solid solutions, and their emission bands slightly red-shift from 500 nm to 509 nm due to the local structure relaxation. Doping Ca2+ would inhibit the growth of SrMoO4 solid solution crystallites to result in smaller size crystallization. The smaller the particle sizes of the solid solutions, the higher their PL intensity.Pure SrMoO4, and SrMoO4 solid solution crystallites can be easily synthesized by a simple electrochemical process. The formation of Ca2+ doped solid solutions effectively enhances the photoluminescence (PL) of SrMoO4, and their PL intensity gradually strengthens with an increase of Ca2+ concentration.Display Omitted► Electrochemical route to Ca2+ doped SrMoO4 solid solution crystallites. ► Ca2+ doping enhances the photoluminescence of SrMoO4 effectively ► Ca2+ inhibits the growth of the solid solution crystallites.
Keywords: Photoluminescence; Electrochemical process; SrMoO4;

8-Hydroxyquinoline-5-carbaldehyde Schiff-base as a highly selective and sensitive Al3+ sensor in weak acid aqueous medium by Xin-hui Jiang; Bao-dui Wang; Zheng-yin Yang; Yong-chun Liu; Tian-rong Li; Zeng-chen Liu (1224-1227).
In the paper, a novel fluorescent sensor (1) based on 8-hydroxyquinoline carbaldehyde Schiff-base was synthesized and characterized. This fluorescent sensor exhibited high selectivity for Al3+ over other metal ions with the detection limit reaching below 10− 7  M under weak acid aqueous conditions. These suggested that 1 could be served as a highly selective and sensitive fluorescence sensor for aluminum ion in acid medium.A novel fluorescent sensor (1) based on 8-hydroxyquinoline carbaldehyde Schiff-base was synthesized and characterized. This fluorescent sensor exhibited high selectivity for Al3+ over other metal ions with the detection limit reaching below 10− 7  M under weak acid aqueous conditions.Display Omitted►A novel 8-hydroxyquinoline carbaldehyde Schiff-base is synthesized. ►The Schiff-base exhibits higher selectivity and sensitivity for Al3+ in acid aqueous medium. ►The fluorescence sensor can be synthesized and performed easily.
Keywords: Aluminum ion; Fluorescence sensor; Crystal structure; 8-Hydroxyquinoline; Schiff-base;

The first Mn–Zn heterometallic dinuclear compound based on Schiff base ligand N, N′-bis(salicylidene)-1,3-diaminopropane by Yue-Nan Chen; Ying-Ying Ge; Wei Zhou; Liu-Fang Ye; Zhi-Gang Gu; Guo-Zheng Ma; Wei-Shan Li; Hong Li; Yue-Peng Cai (1228-1232).
One new heterometallic dinuclear Schiff-base complex Mn(DMF)2Zn(salpn)Cl2 (1) (H2salpn = N,N′-bis(salicylidene)-1,3-diaminopropane) has been successfully constructed by the solvothermal reaction of Mn(ClO4)2, ZnCl2 and H2salpn, and characterized by element analysis, IR spectroscopy and thermal analysis, as well as single crystal X-ray diffraction. The result reveals that compound 1 is heterodinuclear with Mn2+ and Zn2+ centers, in which they respectively present octahedral and tetrahedral coordination geometries. Each neutral molecule unit [Mn(DMF)2Zn(salpn)Cl2] is further connected by four intermolecular hydrogen bonding C―H⋅⋅⋅Cl and two C―H⋅⋅⋅O interactions from six adjacent units to form a three-dimensional supramolecular network with pcu α-Po 412⋅ 63 topology. Moreover, luminescence, antifungal and antimicrobial activities of the heteronuclear compound 1 have also been investigated.A three-dimensional supramolecular network with pcu α-Po 412⋅ 63 topology assembled from neutral molecule unit [Mn(DMF)2Zn(salpn)Cl2] (1) by four intermolecular hydrogen bonding C―H⋅⋅⋅Cl and two C―H⋅⋅⋅O interactions, in which complex 1 denotes the first example of the hetero-dinuclear Mn–Zn compound containing H2salpn ligand.Display Omitted► The first heterometallic dinuclear complex [MnZn(salpn)Cl2] was constructed from alone Schiff base ligand H2salpn, which was assembled into 3D supramolecular network with 6-connected pcu α-Po type 412·63 topology. ► Though many mononuclear, dinuclear and trinuclear Zn2+/Mn2+ complexes as well as 1D Zn2+/Mn2+ polymers derived from the Schiff base ligand N, N′-bis(salicylidene)-1,3-propanediamine, with the various anions or solvent molecules acted as the bridging or terminal groups have been widely investigated at recent years, its heterometallic dinuclear Mn-Zn complexes are not reported so far. ► To the best of our knowledge, the compounds Mn(DMF)2Zn(salpn)Cl2 (1) (H2salpn = N,N′-bis(salicylidene)-1,3-diaminopropane) is the first example of the hetero-dinuclear Mn-Zn compound containing H2salpn ligand.
Keywords: 0-D Mn–Zn heterometallic complexes; N,N′-bis(salicylidene)-1,3-diamino-propane; Antifungal and antimicrobial activities; Fluorescence;

Fabrication of hollow zeolite spheres using oil/water emulsions as templates by Nailin Yue; Ming Xue; Shilun Qiu (1233-1236).
Hollow zeolite spheres of silicalite-1 with monolayered, homogeneous and dense zeolitic shells have been synthesized using oil/water emulsions as templates for the first time. As-prepared spheres are stable and can keep intact after calcination. Additionally, the morphology and N2 adsorption have been characterized.Hollow zeolite spheres of silicalite-1 with monolayered, homogeneous and dense zeolitic shells were synthesized by the combination of emulsions and hydrothermal treatment for the first time.Display Omitted► Hollow silicalite-1 spheres have been synthesized using oil/water emulsions. Silicalite-1 nanocrystals act as both the emulsifier and stabilizer in emulsions. Oil phase acts as a template in the formation of zeolite spheres.
Keywords: Silicalite-1 zeolite; Hollow spheres; Emulsion;

Two isomorphous cobalt(II) and nickel(II) complexes with mixed ligands formulated as [M(bpmp)(aip)]·3H2O (M = Co, 1; M = Ni, 2) (H2aip = 5-aminoisophthalic acid, bpmp =  N,N′- bis - (4-pyridyl-methyl) piperazine) have been obtained under hydrothermal condition. X-ray diffraction analyses indicate that 1 and 2 are isomorphous and both of them hold new binodal (3,5) connected network with the Schläfli symbol of (63)(67.83). Magnetic measurement of 1 reveals that it exhibits antiferromagnetic coupling interaction.Two 3D binodal (3,5) connected networks with the Schläfli symbol of (63)(67.83) assembled from mixed flexible neutral ligands and rigid charge compensated ligand system are reported.Display Omitted► 3D binodal (3,5) connected network with the Schläfli symbol of (63)(67.83). ► Coordination networks assembled from mixed ligands. ► Mixed flexible neutral ligands and rigid charge compensated ligand system.
Keywords: Coordination polymer; Cobalt(II) complex; Nickel(II) complex; Bipyridyl ligand;

A highly selective fluorescent chemosensor for Cd(II) based on 8-hydroxyquinoline platform by Zhenpeng Li; Pinxian Xi; Liang Huang; Guoqiang Xie; Yanjun Shi; Hongyan Liu; Min Xu; Fengjuan Chen; Zhengzhi Zeng (1241-1244).
Tris[2-(8-chinolinyloxy)ethyl]amine (L) has been developed as a highly selective fluorescent chemosensor for Cd2+ based on the chelation-enhanced fluorescence (CHEF) mechanism. Its sensing behavior toward metal ions was investigated by absorption and fluorescence spectroscopy. In buffer solution (10 mM Tris–HCl, pH = 7.4) of L, the presence of Cd2+ induces the formation of a metal–ligand (Cd2+–L) complex, which exhibits a strong, increasing fluorescent emission centered at 417 nm. The binding mode of the Cd2+–L complex has been found to be 1:1 based on the fluorescence/absorption titration and further confirmed by X-ray crystallography.Tris[2-(8-chinolinyloxy)ethyl]amine (L) has been developed as a highly selective fluorescent chemosensor for Cd2+ based on the chelation-enhanced fluorescence (CHEF) mechanism. X-ray crystal structure of cadmium complex revealed that the coordination form of L and Cd(II) is 1:1.Display Omitted► A novel fluorescent sensor L based on the 8-hydroxylquinoline platform has been developed. ► This sensor exhibited high sensitivity and selectivity for Cd2+ over other metal ions. ► Probe L could effectively detect Cd2+ in a wide pH range (pH 4–11). ► The 1:1 coordinative formation between L and Cd(II) was demonstrated by X-ray crystal diffraction.
Keywords: Fluorescent sensor; 8-Hydroxyquinoline; Cadmium; Crystal structure;

Synthesis, crystal structures and luminescence properties of two novel 3D heterometallic coordination polymers by Wan-zhong Zhang; Tian-yi Lv; De-zhou Wei; Rui Xu; Gang Xiong; Yu-qi Wang; En-jun Gao; Ya-guang Sun (1245-1249).
Two heterometallic coordination polymers, {KBa(ptc)(H2O)2}n(1) and {KCaEr(ptc)2(H2O)}n(2) (H3ptc = pyridine-2,4,6-tricarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR and single crystal X-ray diffraction. 1 and 2 exhibit two novel three-dimensional (3D) frameworks, and the luminescence properties of 1, 2 were investigated.By using the pyridine-2,4,6-tricarboxylic acid ligand under hydrothermal strategy, two heterometallic coordination polymers {KBa(ptc)(H2O)2}n (1) and {KCaEr(ptc)2(H2O)}n (2) were successfully synthesized, which obtained three kinds of coordinated modes of the ligand. Furthermore, both 1 and 2 show favorable luminescence properties at room temperature.Display Omitted► Two new HMCPs {KBa(ptc)(H2O)2}n(1) and {KCaEr(ptc)2(H2O)}n(2) have been synthesized by hydrothermally reaction based on the H3ptc (H3ptc=pyridine-2,4,6-tricarboxylic acid). ► Complex 2 is the first example of Er(III)-Ca(II)-K(I) HMCPs based on H3ptc. ► Complexes 1 and 2 show photoluminescence property at room temperature.
Keywords: Heterometallic; Coordination polymers; Crystal structure; Luminescence;

The chiral coordination polymer [Co2(D-cmph)2(4-bpmp)] n (1, D-cmph =  D-camphorate, 4-bpmp = bis(4-pyridylmethyl)piperazine) exhibits [Co2(D-cmph)2] n layers with embedded {Co2(OCO)4} equatorial–equatorial bridged paddlewheel clusters. The long-spanning dipyridyl tethering ligands link the layers into a 6-connected 3-D self-penetrated network with 446108 mab topology, in which shortest 6-membered circuits are penetrated by two others. High thermal stability is observed for the self-penetrated network. Antiferromagnetic coupling (J  =  3.9(1) cm− 1) is observed in 1.The chiral coordination polymer [Co2(D-cmph)2(4-bpmp)] n (1, D-cmph =  D-camphorate, 4-bpmp = bis(4-pyridylmethyl)piperazine) has a 6-connected 3-D self-penetrated mab network with embedded antiferromagnetically coupled {Co2(OCO)4} equatorial–equatorial bridged paddlewheel clusters.Display Omitted► Chiral cobalt coordination polymer layers with D-camphorate. ► Cross-pillared by bis(4-pyridylmethyl)piperazine into self-penetrated mab net. ► Antiferromagnetic coupling within embedded {Co2(OCO)4} clusters. ► High thermal stability.
Keywords: Coordination polymer; Cobalt; Self-penetration; Crystal structure; Antiferromagnetism;

Zinc(II)phthalocyanine as an optical window for visible region by İbrahim Özçeşmeci; Idris Sorar; Ahmet Gül (1254-1257).
Zinc(II)phthalocyanine with four naphthoxy pendant groups on the periphery was prepared by cyclotetramerization of 4-(2-naphthoxy)phthalonitrile. Thin films of this material have been prepared from solutions of different concentrations (5–100 mg ZnPc in 1 mL THF) by spin coating technique. Optical transmittance of thin films was measured using a spectrophotometer in the wavelength range of 260–1100 nm. Results show that transmittance is decreased with the increasing concentration in the ranges corresponding to B and Q absorptions, but the films can still be proposed as optical windows between these regions (~ 400–600 nm) due to very low absorbances. The surface morphology of the thin films was investigated by atomic force microscopy, AFM, and showed that all of the films have nano volcanic holes, except the film prepared from the most concentrated solution (100 mg ZnPc in 1 mL THF).A new zinc(II) phthalocyanine derivative with four naphthoxy pendant groups on the periphery has been synthesized. Thin films of this compound prepared by spin coating technique have been studied in the spectral range of 260–1100 nm. This material can be used as optic filters between 300–400 nm and 600–700 nm and also it can maintain a wide optical window in the visible range from 400 to 600 nm.Display Omitted► Zinc(II)phthalocyanine with 2-naphthoxy substituents on the periphery was achived by cyclotetramerization of corresponding phthalonitrile derivative. ► Thin films of this compound have been obtained by spin coating on 2947 Corning glass substrates. ► Transmittance spectra of the films show specific regions of high and low absorption values suitable for optic filters or optic windows. ► Films prepared from less concentrated solutions are leading to higher surface areas suitable for catalytic and sensor applications.
Keywords: Phthalocyanine films; Zinc; 2-Naphthol; Optical properties;

Two novel d10 metal coordination polymers [Cd(3,5-PMBC)2(H2O)2] (1) and {[Zn(3,5-PMBC)2(H2O)2]⋅2H2O} (2) (3,5-PMBC = 3-pyrimidin-5-ylbenzoic acid) have been synthesized under solvothermal conditions, and characterized by IR spectroscopy, powder and single crystal X-ray diffractions. In 1 and 2, the d10 metal ions (Zn2+ and Cd2+) directed the self-assemblies to form two types of significantly different coordination structures: 1 exhibits one-dimensional double-stranded chain, while 2 displays a unique two-dimensional undulated double layer. Both are further stacked via hydrogen-bond interactions to assemble three-dimensional supramolecular structures. Thermal and photoluminescent properties of 1 and 2 are also investigated in details.Two novel d10 metal-directed coordination polymers [Cd(3,5-PMBC)2(H2O)2] (1) and {[Zn(3,5-PMBC)2(H2O)2]2H2O} (2) have been prepared and characterized. compound 1 exhibits one-dimensional double-stranded chain, while 2 displays an unique two-dimensional undulated double layer. Both are further stacked via hydrogen-bond interactions to form three dimensional supramolecular structures.Display Omitted► Coordination polymers based on the unsymmetric ligand 3-pyrimidin-5-ylbenzoic acid are not reported so far. ► The first two novel d10 metal coordination polymers [Cd(3,5-PMBC)2(H2O)2] (1) and {[Zn(3,5-PMBC)2(H2O)2]2H2O} (2) (3,5-PMBC = 3-pyrimidin-5-ylbenzolate) have been synthesized and structurally characterized. ► The strong fluorescence emissions for 1 and 2 have been observed in the solid state.
Keywords: Coordination polymer; Unsymmetric ligand; Crystal structure; d10 metal; Photoluminescence;

Tetrameric complexes of the composition [MO(L1)]4 (M = Tc, Re), where (L1)3– represents an asymmetric, trianionic cyclisation product with thiocarbamoylbenzamidinato and mercaptotriazolato donor sites, were formed during reactions of [TcOCl4] or [ReOCl4] with a potentially multidentate ligand derived from thiocarbohydrazide and N-[N',N'-diethylamino(thiocarbonyl)]benzimidoyl chloride.Display Omitted► A bridging SNS/S ligand is formed under the influence of metal ions. ► Tetrameric Tc and Re complexes were isolated. ► The crystal structures of the products were determined.
Keywords: Technetium; Rhenium; Oxo complex; Cyclisation; X-ray structure;

Three Cd(II)-btc coordination polymers exhibiting different networks which are affected by co-ligands such as Acridine (L 1 ), Phenanthridine (L 2 ) and Quinoline (L 3 ): 2-D (4,4) net for [Cd(Hbtc)2(HL1)2] (1), 2-D double-layer for [Cd3(btc)2(L2)2(H2O)2].2H2O (2) and 3-D net for [Cd(btc)(HL3).H2O].2H2O (3).Cd(II)-btc coordination polymers (H3btc = benzene-1,3,5-tricarboxylic acid) containing different heterocyclic aromatic co-ligands have been isolated under hydrothermal conditions. Each polymer shows different network because the co-ligand might serves as the structure-directing template.Display Omitted► Three new cadmium coordination polymers based on benzene-1,3,5-tricarboxylic acid. ► Different networks are affected by heterocyclic aromatic co-ligands. ► One polymer is a 2-D (4,4) net. ► One polymer is a 2-D double-layer. ► The third one is a 3-D net.
Keywords: Cadmium(II) complex; Coordination polymers; Benzene-1,3,5-tricarboxylic acid; Heterocyclic co-ligands;

A new three-dimensional phosphate by the synergy of five-coordinated and six-coordinated vanadium, has been obtained. Compared with other V–P–O systems, large cavity and polynuclear transition metal are co-existed in the new compound, which is rarely reported.A new 3D vanadium oxide phosphate compound (H2en)2{V(H2O)2[(V2O2)2(OH)2(HPO4)2(PO4)2]2}·4H2O (1) has been synthesized and characterized. Its electrochemical and magnetic properties were studied. In order to verify and interpret the cavities of the compound (1), the property of N2 adsorption was also pulled in as means of assisting.Display Omitted► In this study, we report a new three-dimensional vanadium phosphate. ► We study electrochemical and magnetic properties of a new phosphate and polynuclear vanadium. ► In this study,we can see that the three-dimensional structure have large cavities.
Keywords: Polyoxometalates; Hydrothermal synthesis; Crystal structure; Magnetic property;

Bulk solvent-free melt ring-opening polymerization (ROP) of L-lactide catalyzed by Ni(II) and Ni(II)–Ln(III) complexes based on the acyclic Salen-type Schiff-base ligand by Liqin Ding; Wenjuan Jin; Zeng Chu; Leilei Chen; Xingqiang Lü; Guanbao Yuan; Jirong Song; Daidi Fan; Feng Bao (1274-1278).
A monometallic (Ni2+, 1) and a series of heterometallic (Ni2+–Ln3+, Ln = Ce (2); Ln = Nd (3); Ln = Sm (4); Ln = Eu (5); Ln = Tb (6); Ln = Ho (7); Ln = Tm (8)) complexes based on the acyclic Salen-type Schiff-base ligands H 2 L (H 2 L = N,N′-bis(3-methoxysalicylidene)propane-1,2-diamine) were synthesized and characterized by FT-IR, ESI-MS and X-ray crystallography. The catalysis results showed that the two kinds of complexes with different active species, could efficiently catalyze the bulk solvent-free melt ring-opening polymerization (ROP) of l-lactide with moderate molecular weights and narrow molecular weight distributions. Especially for the series of bimetallic complexes 28, the involvement of rare ions slightly decreased the catalytic activities on the ROP of l-lactide, while was in favor of the increase of polymeric molecular weights (Mw or Mn) and the polymerization controllability, and the type of rare ions was important and influential factor contributing to the catalytic behaviors.A monometallic (Ni2+, 1) and a series of bimetallic (Ni2+–Ln3+, Ln = Ce, 2; Ln = Nd, 3; Ln = Sm, 4; Ln = Eu, 5; Ln = Tb, 6; Ln = Ho, 7; Ln = Tm, 8) Salen-type Schiff-base complexes with different reactive species, could efficiently catalyze the bulk solvent-free melt ring-opening polymerization (ROP) of l-lactide. Especially for the bimetallic complexes 28, the involvement of rare earth ion was important and influential to the catalytic behaviors.Display Omitted► Ni2+ or Ni2+ –Ln3+ complexes as the catalysts for bulk solvent-free melt ring-opening polymerization (ROP) of l-lactide. ► Intramolecular Ni···Ln separations being relative to the catalysis. ► Coordination geometry and electrophilicity or Lewis acidity of active species.
Keywords: Acyclic Salen-type Schiff-base d or d–f complex; Bulk solvent-free melt ring-opening polymerization; l-lactide;

Two new niobium phosphates KNbP2O8 (1) and NbPO4F2 (2) were synthesized by using a two-step hydro/solvothermal procedure and structurally characterized by sing-crystal X-ray diffractions. Both compounds are based on the alternative connection of Nb-octahedra and P-tetrahedra to form extended three-dimensional solids with different local interruptions around polyhedral sites. Compound 1 features a (3,6)-connected microporous anionic framework exhibiting local interruptions around the P-tetrahedra, and compound 2 gives a 4-connected dense solid with local interruptions around the Nb-octahedra.Two new inorganic niobium phosphates KNbP2O8 and NbPO4F2 were synthesized by using a two-step hydro/solvothermal route. Both compounds are formed by the alternative connection of Nb-octahedra and P-tetrahedra to give a (3,6)-connected microporous framework with anatase topology and a 4-connected dense solid with cag topology, respectively, which result from different local interruptions around polyhedral sites.Display Omitted► A two-step solvothermal route was used to synthesize niobium phosphates. ► The ingredients of porous phosphates further reach the second row transition metals. ► The diversities of niobium phosphates can result from different local interruptions. ► Microporous phosphate displays good ion-exchange capacity.
Keywords: Niobium phosphate; Microporous materials; Hydrothermal synthesis; Interrupted structure;

Water structure: A rare 3D water-chlorin architecture by Gong-ming Sun; Jin Zou; Zhen-wei Liao; Gui-le Yan; Hai-xiao Huang; Shu-juan Liu; Feng Luo (1283-1285).
In this work, we report a new Co(II) compound, namely Co(L)2(Cl)2 ·7H2O(1) featuring a 1D tape structure, was obtained by hydrothermal self-assembly of CoCl2 and 2,4,5-tri(4-pyridyl)-imidazole (L). The structure feature of it is the 3D water-chlorin architecture based on two kinds of chain-like water structures classified by the C4 and T4(0)A2 pattern, respectively.The guest water molecules observed in 1 display two kinds of structural patterns, C4 vs. T4(0)A2. Further, with the consideration of O–H…Cl hydrogen bonds, these C4 and T4(0)A2 water structure are combined together to give a highly rare 3D water-chlorin architecture.Display Omitted► A novel water-chlorin architecture is presented here. ► Both C4 and T4(0)A2 water structure is the basic unit. ► The potential porosity is also notable.
Keywords: Hydrothermal synthesis; Co(II) compound; Water structure;

Two new thioantimonates [Co(dien)2]4[CoSb6S14] (1) and [Co(dien)2]2[Sb4S9] (2, dien = diethylenediamine) were solvothermally synthesized by the reactions of Co, Sb and S in dien at 160 °C. 1 is composed of heterometallic [CoSb6S14]8− anion built up from the connection of one [CoS4] tetrahedron and two [SbIII 3S7] units sharing edges, while 2 contains 1-D mixed-valent thioantimonate anion [Sb4S9 4−]n constructed by the connection of the [SbIII 3S7] units and the SbVS4 tetrahedra sharing corners. The optical properties of 1 and 2 have been investigated by UV–Vis spectra.Two new thioantimonates [Co(dien)2]4[CoSb6S14] (1) and [Co(dien)2]2[Sb4S9] (2) were solvothermally synthesized by the reactions of Co, Sb, S and dien. The different thioantimonate anions are closely related to the different conformation of [Co(dien)2]2+ cation.Display Omitted► The majority of solvothermal reactions carried out in the presence of d-block TM ions result in the formation of isolated Sb x S y m- frameworks combined with TM complex cations as counterions, but whole d-block TM ion encapsulated within the thioantimonate anion was relatively rare, 1 is the only example of two [SbIII 3S7] units sharing two edges with one CoS4 tetrahedran. ► Moreover, the coexistence of SbIII and SbV in a thioantimonate anion was less observed. ► 2 is characterized a new 1-D mixed-valent thioantimonate anion [Sb4S9 4-]n based on the combination of the [SbIII 3S7] units and the SbVS4 tetrahedra.
Keywords: Solvothermal synthesis; Thioantimonates; Transition-metal complexes; Crystal structures;

Mixed-valent tetranuclear manganese complexes with an {MnII 3MnIV} core by Małgorzata Hołyńska; Stefanie Dehnen (1290-1293).
Two new examples of mixed-valent phenyl 2-pyridyl ketoxime complexes with an {MnII 3MnIV4-O} core are presented: cationic {MnII 3MnIVO(OH)[Ph(py)CNO]3[Ph(py)CNOH](ClC6H4COO)3}+ (1) and neutral {MnII 3MnIVO[Ph(py)CNO]4(IC6H4COO)4} (2), representing two different structural types (types I and II, respectively). Also preliminary data are mentioned for two further complexes with (2-pyrimidylthio)acetate (3) or 2-(methylthio)nicotinate (4) ligands. 1 and 2 differ in magnetic properties, 1 representing the first {MnII 3MnIV4-O}-core cationic complex with dominating antiferromagnetic interactions.The title compounds represent two new examples of mixed-valent phenyl 2-pyridyl ketoxime complexes with an {MnII 3MnIV4-O} core, representing two different structural types and different magnetic properties, and including the first {MnII 3MnIV4-O}-core cationic complex with dominating antiferromagnetic interactions.Display Omitted► Mixed-valent phenyl 2-pyridyl ketoxime complexes with an {MnII 3MnIV4-O} core. ► Different magnetisms as a function of differing structural details. ► First {MnII 3MnIV4-O}-core cationic complex with dominating antiferromagnetic interactions.
Keywords: Mixed-valent complexes; Manganese; Ketoxime ligands; X-ray diffraction; Magnetism;

The dinuclear ruthenium(II) complex [Ru2(CO)2Cl4(THT)2(μ-THT)2], 1, (THT = tetrahydrothiophene) exhibiting bridging thioether ligands yields mononuclear complexes upon treatment with Lewis bases by cleavage of the respective thioether bridges. Reacting 1 with an excess THT leads to the isolation of [RuCl2(THT)4], 2, whereas the reaction with triphenylphosphane produces the mononuclear ruthenium compound [RuCl2(CO)(THT)(PPh3)2], 3. The latter compound was also characterized by X-ray diffraction.The dinuclear ruthenium(II) complex [Ru2(CO)2Cl4(THT)2(μ-THT)2], 1, (THT = tetrahydrothiophene) exhibiting bridging thioether ligands yields mononuclear complexes upon treatment with Lewis bases by cleavage of the respective thioether bridges. Reacting 1 with an excess THT leads to the isolation of [RuCl2(THT)4], 2, whereas the reaction with triphenylphosphane produces the mononuclear ruthenium compound [RuCl2(CO)(THT)(PPh3)2], 3.Display Omitted► The dinuclear substrate [Ru2(CO)2Cl4(THT)2(μ-THT)2] is easily available. ► Thioether bridges might be cleaved by various Lewis bases. ► Mononuclear Ru(II) complexes are produced in excellent yields.
Keywords: Ruthenium; Tetrahydrothiophene; Triphenylphosphane; X-ray;

Synthesis, characterization and crystal structure of a new fluorescent probe based on Schiff Base for the detection of Zinc (II) by Shan-bin Liu; Cai-feng Bi; Yu-hua Fan; Yu Zhao; Peng-fei Zhang; Qing-dan Luo; Dong-mei Zhang (1297-1301).
A Schiff base compound (L) was synthesized using o-vanillin and 4, 4′-diaminodiphenylmethane and characterized by elemental analysis, 1H NMR, 13C NMR, IR, electronic absorption spectra and X-ray diffraction single crystal analysis. The title compound(L) has no fluorescence intensity in a range of 450–650 nm, but its fluorescence spectrum shows enhancement in the intensity of the signal at 372 nm on binding with the Zn(II) cation from pH = 6 to 14. No such significant change was observed for other metal ions. Fluorescence intensity was linear with concentration of Zn (II) cation in a range from 1 × 10− 7  mol·L− 1 to 1.2 × 10− 5  mol·L− 1. This Schiff base compound is a promising system for the development of new fluorescent probes for the detection of Zn (II) cation.A Schiff base was synthesized and characterized and determined by elemental analysis, 1H NMR, 13C NMR, IR, electronic absorption spectra and X-ray diffraction single crystal analysis. It was found that this Schiff base compound is promising system for the development of new fluorescent probes for the detection of Zn (II) cation.Display Omitted► This Schiff base can be used as a new fluorescent probes for the detection of Zn (II) cation. ► The crystal structures and molecular structure of Schiff base ligand was determined by single-crystal X-ray diffraction. ► This Schiff base compound is promising system for the development of new fluorescent probes for the detection of Zn (II) cation.
Keywords: Fluorescent probe; Zn (II); Schiff base; 4, 4′-diaminodiphenylmethane;

Using a flexible bis-triazole ligand 1,4-bis(1,2,4-triazol-1-y1)butane (btrb), two new copper(II) compounds [Cu0.5(btrb)0.5Cl]n (1) and [Cu0.5(btrb)Cl]n (2), have been isolated. Conformations of btrb can be tuned as a result of changing the metal/ligand ratio in the reaction system, which ultimately forms two novel framework structures. 1 is a three dimensional network with CdSO4 topology, and uncommonly six-fold Cl…H–C hydrogen bonds reside in the 3D framework. 2 possesses 2D (4.4) net framewok. Triple Cl…H–C hydrogen bonds reside among the 2D layers, which link the 2D layers to lead to a 3D supramolecular architecture. For 1 and 2, elemental analysis, thermal stability and EPR spectra have been carried out, and the conformational variation of btrb also has been discussed.Display Omitted► 2D and 3D coordination polymers were isolated by tuning reaction conditions. ► The conformations of btrb ligands can be affected by the metal/ligand ratio. ► The coordination mode of the btrb changes with the conformation’s variation. ► Two different frameworks have been isolated.
Keywords: 1,4-bis(1,2,4-triazol-1-y1)butane; Ligand conformation; Crystal structure; EPR spectra;

The synthesis and characterization of a novel cyclometalated Iridium(III) complex [IrCl(H)(PSiP)] containing monoanionic, tridentate coordinating PSiP-pincer ligands [κ3-(2-tBu2PC6H4)2SiMe] ([PSiP]) is reported. Complex (3) is one of the few examples of bis(phosphino)silyl(hydrido)iridium(III) complexes structurally characterized by single crystal X-ray analysis. This compound has also been shown to catalyze the transfer hydrogenation of ketones to the corresponding secondary alcohols moderately with 2-propanol as the hydrogen source instead of using molecular dihydrogen gas or hazardous reducing agents (e.g., NaBH4 and LiAlH4), and tBuOK as the base.The synthesis and characterization of a novel cyclometalated Iridium(III) complex [IrCl(H)(PSiP)] (3) containing monoanionic, tridentate coordinating PSiP-pincer ligands [κ3-(2-tBu2PC6H4)2SiMe] ([PSiP]) is reported. Complex (3) is one of the few examples of bis(phosphino)silyl(hydrido)iridium(III) complexes structurally characterized by single crystal X-ray analysis. This compound has also been shown to catalyze the transfer hydrogenation of ketones to the corresponding secondary alcohols moderately with 2-propanol as the hydrogen source instead of using molecular dihydrogen gas or hazardous reducing agents (e.g., NaBH4 and LiAlH4), and tBuOK as the base.Display Omitted► A novel cyclometalated Ru(II) complex. ► The first example of halogenated Ru(II) complexes supported by (cyclohexylphosphino)silyl ligand. ► Catalyst for the transfer hydrogenation of ketones to alcohols.
Keywords: Iridium; Silyl; Pincer; Transfer hydrogenation; Tridentate ligands;