Synthesis and Structural Characterization of Gd（Ⅱ） Coordination Polymer [Gd2（μ-phth）3（b-pd）（H2O）5]n

1 INTRODUCTION The polymeric metal complexes with extended structures are of great interest because of their useful chemical or physical properties[1]. Due to the noti- ceable fact that the aromatic polycarboxylate can provide versatile coordination mode and the non- coplanar structure of carboxylate groups and benze- ne rings, a lot of efforts in this field have been parti- cularly directed to the preparation of aromatic poly- carboxylate (such as phthalate, terephthalate and isophthalat…     

[Et_4N]_2[Zn_2(OPh)_2Cl_4]的合成和晶体结构

ZnCl2, PhONa和Et4NCl稨2O在乙腈溶剂中反应合成了一种二核锌配合物[Et4N]2[Zn2(OPh)2Cl4]。X射线衍射结果表明,晶体属单斜晶系,C2/m空间群,晶胞参数 a = 14.1366(2), b=13.6985(5), c=9.3308(3)牛?107.851(2)o, V=1719.92(9)?,C28H50O2N2Zn2Cl4,Mr=721.24,Z=2,Dx=1.393g/cm3,μ(MoKα)=1.732mm—1,F(000)=756, R=0.0552, wR=0.1534, S=1.027。 配合物是由2个阳离子Et4N+和1个阴离子[Zn2(OPh)2Cl4]2—组成。阴离子[Zn2(OPh)2Cl4]2—包含着1个中心Zn2O2菱形平面。配合物中的2个锌原子通过2个苯酚中的氧原子桥连,每个锌原子还与2个氯原子配位形成变形四面体结构。     

Synthesis and Crystal Structure of a Novel Two-dimensional Layered Polymer

The title complex [Zn(μ-O2CCH=CHCO2)(C3H4N2)(H2O)]n was prepared by the reaction of zinc carbonate with maleic acid and imidazole in an aqueous-alcohol solution at 333 K, and its crystal structure has been solved by single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group Pc with a = 5.3858(7), b = 22.685(3), c =7.6782(1) A, β = 92.261(2)°, V = 937.4(2) A3, Z = 1, C14H16N4O10Zn2, Mr= 531.05, Dc= 1.882g/cm3,μ = 2.623 mm-1, F(000) = 532, the final R = 0.0372 and wR = 0.0930 for 1926 observed reflections with I＞2σ(I). The central zinc atom is five-coordinated in a distorted square pyramidal environment to three oxygen atoms of two different maleate ligands, a nitrogen atom of the imidazole ligand and an oxygen atom of water. In the complex two carboxylate groups of the maleate ligands have two coordination modes. One acts as a bidentate chelate ligand and the other a monoatomic monodentate ligand to bridge two zinc centers. As a result, 1-D infinite polymeric coordination water OH groups and carboxylate oxygen atoms to construct a 2-D layered polymer,and the layer structure is stabilized by π-π stacking of the imidozel ligands.     

Synthesis and Structure of a Manganese(Ⅱ) Complex [Mn·(p-Methoxybenzoato)_2·(2,2'-bipy)·H_2O]·(p-methoxybenzoic Acid)

The title compound,{[MnL2·(2,2'-bipy)·H2O]·(HL)},has been synthesized (HL =p-methoxybenzoic acid,2,2'-bipy = 2,2'-bipyridine) by the reaction of MnCl2·6H2O with p-methoxybenzoic and 2,2'-bipyridine in an alcohol-water solution.It crystallizes in the triclinic system,space group P1 with a = 10.1138(5),b = 11.2811(5),c = 16.2210(8)(A),a = 77.5920(10),β= 72.1890(10),γ = 66.2320(10)°,Mr = 683.56,V= 1603.65(13) (A)3,Z= 2,Dc = 1.416 g/cm3,F(000)= 710,μ =0.473 mm-1,the final R = 0.0619 and wR = 0.1571 for 4724 observed reflections with I ＞ 2σ(I).The structure determined demonstrated that it is an isomeric modification of the structure reported before.The Mn atom is six-coordinated by two N and four O atoms,forming a distorted octahedral geometry.All Mn-O and Mn-N distances range from 2.113(3)～2.410(3) (A).There also.exists a dissociative p-methoxybenzoic acid beside the octahedron.     

一对杂环异构体作为配体与Ag(Ⅰ)的配位化学研究：合成、晶体结构和荧光表征

成功合成并分离了一对异构的杂环配体L₁和L₂(L₁=1-((吡啶-4-基)甲基)-1氢-苯并三唑,L₂=2-((吡啶-4-基)甲基)-1氢-苯并三唑))。这类配体在构筑复杂的金属有机框架方面,具有许多优点。把这对配体分别和高氯酸银作用,得到了2个新的化合物1和2并测定了结构,分别为[Ag(L₁)(ClO₄)]_n(1)和[Ag(L₂)₂]ClO₄·H₂O(2)。化合物1为一维双螺旋结构,而化合物2仅仅展现出零维结构。配体在结构上的细微差别可以导致所形成的配位化合物的结构的巨大差异。     

四-β-(氨甲基)酞菁锌盐酸盐的合成及光物理光化学性质研究

四-β-(邻苯二甲酰亚胺甲基)酞菁锌(ZnPcP4)与85%水合肼反应得到四-β-(氨甲基)酞菁锌(ZnPcN4,分子式C36H28N12Zn),其盐酸盐为ZnPcN4.HCl。测试合成得到的标题化合物紫外-可见电子吸收光谱,荧光光谱和单线态氧生成速率。标题化合物在水中聚集,在90%1,2-丙二醇/水中主要以单体形式存在。目标酞菁锌配合物在90%DMF/水的中性溶液存在聚集体,在弱酸性条件下,随酸度增大,675 nm处Q带单体吸收峰升高,在DMF/water(10%,V/V)/HCl(1.2 mmol·L-1)溶液中10-5 mol·L-1的酞菁配合物基本上没有聚集;在强酸性条件下,随酸度增大,675 nm处Q带单体吸收峰下降的同时,在713 nm处酞菁单质子化吸收峰强度有所增加。ZnPcN4.HCl在DMF体系中聚集,荧光量子产率和单线态氧量子产率变小,但其在DMF/water(10%,V/V)/HCl(1.2mmol·L-1)体系中主要以单体形式存在,荧光量子产率为0.19,单线态氧量子产率0.58,光敏活性与标准无取代酞菁锌相近。     

Synthesis and Structural Characterization of Co( Ⅱ ) Coordination Polymer [Co(μ-phth)(imi)2]n

A new cobalt( Ⅱ ) complex [Co(μ-phth)(imi)2]n (phth = o-phthalato, imi = imidazole)has been synthesized by the reaction of CoCl2 with disodium o-phthalate and imidazole. The crystal structure of the compound has been determined by single-crystal X-ray diffraction. The crystal is of monoclinic system, space group Pn with a = 8.405(1), b = 9.995(1), c = 9.996(2) (A),β= 104.479(2),V= 813.0(2) (A)3, Dc= 1.467 g/cm3, C14H12N4O4Co, Mr= 359.21, F(000) = 366,μ = 1.079 mm-1, Z = 2, R = 0.0483 and wR = 0.1209 for 1583 observed reflections (Ⅰ＞ 2σ(Ⅰ)). In the title complex, the Co(Ⅱ) ions are bridged by o-phthalate ligands in a bidentate mode, producing a zigzag infinite chain structure. Each four-coordinated cobalt( Ⅱ ) center was coordinated by two oxygen atoms and two nitrogen atoms to give a distorted tetrahedral geometry. The chains are linked by hydrogen bonds between oxygen atoms belonging to carboxylate groups and hydrogen atoms of imidazole molecules, forming an unusual two-dimensional coordination polymer.     

Investigation of Spectra（NMR,Mass）of Some Fe3S3Cluster Compounds

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二维铅配合物[Pb2(C8H4O4)2(C19H12N4O)2]n·3.5nH2O的水热合成、晶体结构与荧光性质研究

In the title compound, [Pb₂(C₈H₄O₄)₂(C₁₉H₁₂N₄O)₂]_n·3.5nH₂O(1), has been synthesized by the hydrothermal assembly of 1,4-benzenedicarboxylate and 4-(1H-1,3,7,8-tetraazacyclopenta[l]-phenanthren-2-yl)phenol(TCPP) with lead acetate. Elemental analysis, X-ray crystal structure analysis, IR spectrum, thermogravimetric analysis and luminescence property were carried out for the structural determination and characterization of the title compound. Compound 1 crystallizes in triclinic, space group P1 with a=1.013 54(10) nm, b=1.104 84(11) nm, c=1.210 05(12) nm, α=76.812 0(10)°, β=74.814 0(10)°, γ=86.030 0(10)°, V=1.273 1(2) nm³, Pb₂C₅₄H₃₉N₈O_13.5, M_r=1 430.31, Z=1, D_c=1.866 g·cm^-3, μ=6.680 mm^-1, F(000)=691, R=0.027 3 and wR=0.068 7 for 4 042 observed reflections (I>2σ(I)). The compound 1 exhibits two-dimensional network structures, which are further stacked through π-π interactions and hydrogen bonds to form three-dimensional supramolecular polymer. Solid-state luminescent spectrum of the compound 1 indicates intense fluorescent emission. CCDC: 748883.     

Synthesis and Characterization of a Cobalt Complex with Maleate and Pyridine

A new polymeric cobalt complex [Co(u-male)(py)(H2O)]n (male=maleate; py =pyridine) 1 was prepared by cobalt chloride hexahydrate with disodium maleate and pyridine in an alcohol-aqueous solution. Single-crystal X-ray analysis has revealed that 1 crystallizes in the orthorhombic system, space group Pnma with a=18.001(1), b=7.6001(6), c=7.4731(6) A, V=1022.4(1)A3, Z=4, C9H9CoNO5, Mr=270.10, Dc= 1.755 g/cm3, F(000)=548, μ(MoKa)=1.683 mm-1, S =1.002, the final R=0.0280 and wR=0.0746 for 883 observed reflections with I ＞ 2σ(I). The structure analysis shows an approximate octahedral coordination environment of metal center. The Co(Ⅱ) ions are bridged by maleic anions in a rare tetradentate coordination fashion with a syn-anti coplanar conformation of the carboxyl group, forming a two-dimensional corrugated 2-D structure which is further attached into a three-dimensional framework via non-classical C-H…O interactions between adjacent layers.