Syntheses,Crystal Structures and Luminescent Properties of Two Lanthanide Coordination Polymers Based on Bifunctional Ligand

Two lanthanide coordination polymers, [Eu（HL）（L）（H2O）2]n（1） and [Tb（H0.5L）2]n（2）, based on bifunctional 5-（1H-imidazol-1-yl） isophthalic acid（H2L）, are hydrothermally synthesized and characterized by both single-crystal and powder X-ray diffraction analyses, and FT-IR. In compound 1, the basic inorganic building unit of the coordination network is the dinuclear [Eu2（COO）6] cluster. Each [Eu2（COO）6] cluster connects four HL^- ligands and each HLligand links two [Eu2（COO）6] clusters, resulting in a 2D coordination layer. The adjacent 2 D layers are further connected via neighboring inter-layer hydrogen bonds to give a 3D supramolecular structure. In compound 2, the Tb^3＋ is coordinated to six oxygen atoms. Each Tb^3＋ ion connects six ligands and each ligand links three Tb^3＋ ions, leading to a 3D coordination polymeric network which exhibits remarkably high thermal stability up to 500℃. Furthermore, due to the successful incorporation of Tb^3＋, compound 2 displays characteristic luminescent emission in the solid state at room temperature. The combination of high thermal stability and fluorescent property of compound 2 would make it as a promising light-emitting material.

A Chain Cadmium(Ⅱ) Coordination Polymer with Diacylhydrazide: Synthesis,Crystal Structure and Luminescent Property

A novel Cd（Ⅱ） coordination polymer with diacylhydrazide ligand N,N？-bis（3-methoxysalicyl）-2,6-pyridinedicarbohydrazide（H_6msphz）,[Cd_2（H_2msphz）（Py）_4]_n（1,Py = pyridine） has been synthesized through solvothermal reaction and structurally characterized by single-crystal X-ray diffraction,IR,TGA and PXRD investigations. It crystallizes in triclinic system,space group P1,with a = 11.0230（11）,b = 11.7264（15）,c = 17.3395（14） ？,α = 70.520（9）,β = 84.806（7）,γ = 81.965（9）°,V = 2089.9（4） ？~3,Dc = 1.638 gcm^（–3）,μ = 1.083 mm^（-1）,F（000） = 1032,Z = 2 and S = 1.040. In complex 1,the H_2msphz4-ligand uses not only its coordinated pocket to catch one Cd（Ⅱ） ion,but also its two terminal groups to chelate other two Cd（Ⅱ） ions,leading to the formation of a chain structure. The adjacent chains are further assembled together by two kinds of π-π interactions between the Py rings,resulting in the finial double layered supramolecular structure. In addition,complex 1 is found to show photoluminescence in the solid state at room temperature,which can be ascribed to the intraligand π→π＊ transitions.

Hydrothermal Synthesis, Crystal Structure and Luminescent Property of a New Cd(Ⅱ) Coordination Polymer with Four-fold Interpenetrated dia Topology

A new Cd（II） coordination polymer with 2-nitroterephthalie acid （H2npa） and 1,4- bis（2-methyl-imidazol-l-yl） butane （bib） has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction, IR and EA. Complex [Cd（npa）（bib）]n （1） is of orthorhombic system, space group Pcca with a = 16.1750（5）, b = 9.8764（5）, c = 15.5890（3） A, V = 2490.4（2） A3, Z = 4, Mr = 539.82, Dc = 1.440 g/cm3, F（000） = 1088,μ = 0.918 mm-1, the final R = 0.0320 and wR = 0.0775 for 2253 reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that complex 1 displays a four-fold interpenetrated dia topology. Furthermore, the luminescent property for complex 1 is also investigated in solid state at room temperature.

Synthesis and Crystal Structure of a New Zinc(Ⅱ)Coordination Polymer Assembled by 4-Nitrophthalic Acid and Bis(imidazol)Ligands

A new complex [Zn（4-nph）（bib）]（2n）·nH2O（1） has been obtained by the reaction of metal（Zn（Ⅱ））,1,4-bis（imidazol-1-yl）-butane（bib） with 4-nitrophthalic acid（4-H（2nph））.The crystal structure of 1 has been determined by single-crystal X-ray diffraction analysis.Compound 1 is of triclinic system,space group P1 with a = 10.3251,b = 12.4503,c = 16.6497 A,α = 88.487（3）,β = 72.529（3）,γ = 79.991（3）°,V = 2009.8（5）A^3 and Mr = 945.47.Complex 1 shows a three-dimensional（3 D） framework.Moreover,through intermolecular hydrogen bonds,compound 1 is assembled into a supramolecular structure.The thermal stability and luminescent properties of 1 are also investigated.

Structure and Photochemical Properties of a Chiral Cd Coordination Polymer Based on 4,4'-(Hexafluoroisopropylidene)Bis(benzoic acid)and 1,3-Di(pyridineyl)benzene

One new chiral metal-organic coordination polymer,[Cd2（dpb）（H2hfipbb）2]n,was obtained under hydrothermal conditions of 1,3-di（pyridineyl）benzene（dpb） and 4,4＇-（hexafluoroisopropylidene）bis（benzoic acid）（H2hfipbb）. The title compound reveals a three-dimensional（3D） framework with two types of helical chains [Cd（COO）]n,which are linked each other to further form a double helical chain [Cd2（COO）2]n by sharing the same Cd（Ⅱ） ions. The dpb connects the double helical chains to generate a 3D framework. These unique structures were studied by single-crystal X-ray and other spectroscopy techniques. In addition,the luminescent,fluorescence lifetime and second harmonic generation efficiency properties in the solid state have been studied.

A Cd(Ⅱ)Coordination Polymer with cds Topology Constructed by Polycarboxylate and Imidazole-containing Ligand

A new Cd（Ⅱ） coordination polymer,{[Cd（pda）（bimb）]·（H2O）（0.5）}n（1,H2pda=1,3-phenylenediacetic acid,bimb = 4,4-bis（1-imidazolyl）biphenyl）,has been synthesized and characterized by elemental analysis,IR spectroscopy,powder X-ray diffraction（PXRD） analyses and single-crystal X-ray diffraction techniques. Complex 1 shows a 4-connected two-fold interpenetrated three-dimensional（3-D） cds topology. In additional,photoluminescent properties of 1 and its dehydrated product have also been studied.

Syntheses,Structures and Properties for Zn~Ⅱ Coordination Polymers Based on a Functional 4'-(3-Pyridyl)-3,2':6',3''-terpyridine Ligand

Two new Zn~Ⅱ coordination polymers,namely,[Zn L（o-bdc）]n（1） and [Zn L（mbdc）]_n·n H_2O（2）（L = 4？-（3-pyridyl）-3,2？：6？,3？？-terpyridine,H_2（o-bdc） = benzene-1,2-dicarboxylic acid,H_2（m-bdc） = benzene-1,3-dicarboxylic acid）,were synthesized by hydrothermal methods. The crystal structures have been determined by single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic C2/c space group,with a = 28.016（2）,b = 11.3815（11）,c = 19.8071（17） ？,β = 133.961（2）°,V = 4546.2（7） ？3,Z = 8,Mr = 539.83,Dc = 1.577 Mg/m^3,μ = 1.127 mm-1,F（000） = 2208,the final R = 0.0426 and w R = 0.0986 for 2875 observed reflections with I 〉 2σ（I） and displays a 1D coordination chain. While compound 2 crystallizes in monoclinic C2/c space group,with a = 15.6003（14）,b = 11.9152（11）,c = 26.633（3） ？,β = 94.320（2）°,V = 4936.5（8） ？~3,Z = 4,M_r = 1115.67,Dc = 1.496 Mg/m^3,μ = 1.043 mm^（-1）,F（000） = 2272,the final R = 0.0499 and w R = 0.1342 for 2659 observed reflections with I 〉 2σ（I） and shows a classical 3D cds topological network with point symbol of {65.8}. Furthermore,thermal stability and luminescent properties of 1 and 2 have also been investigated.

Syntheses,Structures,and Properties of Three New Polymers Based on Flexible and Rigid Ligands

Three new supramolecular polymers, [（IP）（H2SO4）（H2O）]（1）, [（H2SDC）（BPA）]（2） and [Mn（SDC）（IP）2]n （3）, have been constructed by three modes（rigid IP, rigid SDC ＋ flexible BPA, rigid IP ＋ rigid SDC）. Polymers 1 and 2 are supramolecular structures, assembled by hydrogen bonds and π···π interactions. X-ray structure analysis of 3 shows waved 1D chains which form a 3D supramolecular network by hydrogen bonds and π···π interactions. Solid-state properties of thermal stability, luminescent properties, and X-ray powder diffractions for these crystalline materials have also been investigated, and polymer 3 is considered to be a good stable luminescence material.

Syntheses,structures,luminescent and magnetic properties of two coordination polymers based on a flexible multidentate carboxylate ligand

Two coordination polymers, {[Cu3（tci）2（DMAc）3].6DMAc-2H2O}n （1[） and {[Cu3（tci）2（tpt）2（H2O）2]- 2DMAc-2H2O}n （2） （H3tci = tris（2-carboxyethyl）isocyanurate, tpt = 2,4,6-tris（4-pyridyl）-l,3,5-triazine, DMAc = N,N-dimethylacetamide）, have been constructed under solvothermal conditions. Both polymers were structurally characterized by single crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric （TG） analyses and powder X-ray diffraction （RXPD）. 1 shows a （3,4）-connected 2D layer structure comprising Cu2（CO2）4 paddle-wheel units, which are further bridged by C-H.--O interactions to give a 3D supramolecular network. The introduction oftpt produces different framework for 2 that comprises a dinuclear and a mononuclear Cu（II） building units, which are further bridged together by tci3- and tpt ligands to give a 4-connected 2D topological net. Adjacent 2D layers are packed together via C-H...O interactions and π...π stacking interactions to form a 3D supramolecular structure. In addition, the luminescent properties and the solid-state UV-vis spectra of I and 2 were explored. Furthermore, antiferromagnetic exchange interactions were unveiled in the Cu2（COO）4 units of 1. ~ 2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.