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中性四齿配体导向合成五种Co(II)/Ni(II)配位聚合物:合成、晶体结构及性质

Coligand-directed synthesis of five Co(II)/Ni(II) coordination polymers with a neutral tetradentate ligand: syntheses, crystal structures, and properties.

作者信息

Qin Ling, Wang Zhong-Jie, Wang Ting, Zheng He-Gen, Chen Jin-Xi

机构信息

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, P. R. China.

出版信息

Dalton Trans. 2014 Sep 7;43(33):12528-35. doi: 10.1039/c4dt01535e.

Abstract

The solvothermal reactions of 1,1'-oxybis[3,5-di-4-pyridine]-benzene (L) and transition metal cations (Co and Ni) afford five novel coordination polymers in the presence of flexible bridging ligands (4,4'-H2nba = 4,4'-dicarboxydiphenylamine, H2cam = d-camphoric acid, 4,4'-H2sdb = 4,4'-sulfonyldibenzoic acid, H2chdc = 1,4-trans-cyclohexanedicarboxylic acid), namely {[Co2L2(OH)2(nba)]·2DMF}n (), {[CoL(cam)(H2O)]}n (), {[Co3(L)(4,4'-sdb)3(H2O)]·1.5CH3CN·4H2O}n (), {[Ni3(L)(4,4'-sdb)3(H2O)]·1.5CH3CN·4H2O}n (), and {[Ni2L2(chdc)2(H2O)2]·(H2O)3}n () (DMF = N,N-dimethylformamide). Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectroscopy, and powder X-ray diffraction. Complex reveals a 2-fold interpenetrating three-dimensional (3D) framework with the Schläfli symbol {4·8·10(4)}{4·8·10} topology. Compound crystallizes in the achiral space group with the d-camphorate ligand racemized. Compounds and reveal similar structure with the {3·4(4)·6}{3(2)·4(8)·5(9)·6(9)} topology based on a linear trinuclear building block M3(OOCR)6 (M = Co(ii) or Ni(ii)). Compound is a wavy sheet, where both carboxylate and L ligands act as bidentate ligands. Moreover, UV-Visible absorption spectra of complexes , and the magnetic properties of have been investigated.

摘要

1,1'-氧联双[3,5-二-4-吡啶基]苯(L)与过渡金属阳离子(Co和Ni)的溶剂热反应在柔性桥联配体(4,4'-H₂nba = 4,4'-二羧基二苯胺、H₂cam = d-樟脑酸、4,4'-H₂sdb = 4,4'-磺酰基二苯甲酸、H₂chdc = 1,4-反式环己烷二甲酸)存在下得到了五种新型配位聚合物,即{[Co₂L₂(OH)₂(nba)]·2DMF}ₙ()、{[CoL(cam)(H₂O)]}ₙ()、{[Co₃(L)(4,4'-sdb)₃(H₂O)]·1.5CH₃CN·4H₂O}ₙ()、{[Ni₃(L)(4,4'-sdb)₃(H₂O)]·1.5CH₃CN·4H₂O}ₙ()和{[Ni₂L₂(chdc)₂(H₂O)₂]·(H₂O)₃}ₙ()(DMF = N,N-二甲基甲酰胺)。它们的结构已通过单晶X射线衍射分析确定,并通过元素分析、红外光谱和粉末X射线衍射进一步表征。配合物呈现出具有施莱夫利符号{4·8·10(4)}{4·8·10}拓扑结构的2重互穿三维(3D)骨架。化合物在手性空间群中结晶,d-樟脑酸根配体发生了外消旋化。化合物和呈现出基于线性三核结构单元M₃(OOCR)₆(M = Co(ii)或Ni(ii))的具有{3·4(4)·6}{3(2)·4(8)·5(9)·6(9)}拓扑结构的相似结构。化合物是一种波浪状片层结构,其中羧酸根和L配体均作为双齿配体。此外,还研究了配合物、的紫外可见吸收光谱以及的磁性。

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