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Impact of Isomeric Dicarboxylate Ligands on the Formation of One-Dimensional Coordination Polymers and Metallocycles: A Novel cis→trans Isomerization

机译:异构二羧酸盐配体对一维配位聚合物和金属环形成的影响:一种新型的顺→反异构

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摘要

A series of Co(II), Ni(II) and Cu(II) coordination polymers and dinuclear metallocycles containing 4-aminopyridine (4-ampy) and benzenedicarboxylate ligands, {[M(4-ampy) (1,4-BDC)]·H O·CH CH OH} (M = Ni, ; Co, , 1,4-H BDC = benzene-1,4-dicarboxylic acid), {[Ni (4-ampy) (1,3-BDC) ]·H O·CH CH OH} (1,3-H BDC = benzene-1,3-dicarboxylic acid), , [M (4-ampy) (1,2-BDC) ] (M = Ni, ; Co, , 1,2-H BDC = benzene-1,2-dicarboxylic acid), [Co(4-ampy) (1,3-BDC)] , {[Cu(4-ampy) (1,4-BDC)] CH CH OH} , , and {[Cu(4-ampy) (1,4-BDC)]·H O} , ·H O, are reported, which were hydrothermally prepared and structurally characterized by using single crystal X-ray diffraction. Complexes and are isomorphous 1D zigzag chains, while displays a concave–convex chain and and are dinuclear metallocycles that differ in the boding modes of the 1,2-BDC ligands, forming a 3D and a 2D supramolecular structures with the and topologies, respectively. Complex exhibit a 1D helical chain and complexes and ·H O are 1D linear and zigzag chains, in which the Cu -1,4-BDC units adopt the and configurations, respectively. A novel irreversible structural transformation due to → isomerization of the Cu -1,4-BDC units was observed in ⋅H O and upon water adsorption of the desolvated product of ·H O.
机译:一系列Co(II),Ni(II)和Cu(II)配位聚合物和含有4-氨基吡啶(4-ampy)和苯二羧酸酯配体的双核金属环,{[M(4-ampy)(1,4-BDC) ]·HO·CH CH OH}(M = Ni,; Co,,1,4-H BDC =苯-1,4-二羧酸),{[Ni(4-ampy)(1,3-BDC)] ·HO·CH CH OH}(1,3-H BDC =苯-1,3-二羧酸),,[M(4-ampy)(1,2-BDC)](M = Ni,; Co,, 1,2-H BDC =苯-1,2-二羧酸),[Co(4-ampy)(1,3-BDC)] 报告了{{Cu(4-ampy)(1,4-BDC)] CH CH OH}和{[Cu(4-ampy)(1,4-BDC)]·HO},·HO,通过单晶X射线衍射对它们进行水热制备和结构表征。配合物和是同构的1D之字形链,而显示出凹凸链和和是双核金属环,它们在1,2-BDC配体的键合方式上不同,分别形成3D和2D超分子结构,并带有和拓扑。络合物显示一维螺旋链,而络合物和·HO为一维线性和锯齿形链,其中Cu -1,4-BDC单元分别采用和构型。在·H O中和水吸附·H O的脱溶剂产物后,观察到由于Cu -1,4-BDC单元→异构化而导致的新型不可逆结构转变。

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