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基于异构四羧酸的一系列二价金属配位聚合物:合成、结构及磁性

A series of divalent metal coordination polymers based on isomeric tetracarboxylic acids: synthesis, structures and magnetic properties.

作者信息

Han Min-Le, Duan Ya-Ping, Li Dong-Sheng, Xu Guo-Wang, Wu Ya-Pan, Zhao Jun

机构信息

College of Materials & Chemical Engineering, Collaborative Innovation Center for Microgrid of New Energy of Hubei Province, China Three Gorges University, Yichang, 443002, China.

出版信息

Dalton Trans. 2014 Dec 14;43(46):17519-27. doi: 10.1039/c4dt01946f.

Abstract

Five new coordination polymers, namely, [Mn(2,2′-bipy)(H2O)2(H2L1)]n (1), {[Co(btb)(H2O)2(H2L1)]·0.5H2O}n (2), [Co(bib)(H2O)2(H2L1)]n (3), [Ni2(bpm)(H2O)3(L2)]n (4), and {[Co2(H2O)3(OH)(HL2)]·H2O}n (5), (H4L1 = 1,1′:2′,1′′-terphenyl-4,4′,4′′,5′-tetracarboxylic acid, H4L2 = 1,1′:2′,1′′-terphenyl-3,3′′,4′,5′-tetracarboxylic acid, 2,2′-bipy = 2,2′-bipyridine, btb = 1,4-bis(1,2,4-triazol-1-yl)butane, bib = 1,4-bis(imidazol-1-yl)butane, bpm = bis(4-pyridyl)amine), have been obtained under hydrothermal conditions. Complex 1 exhibits a 3D supramolecular framework based on 1D chains. Both complexes 2 and 3 are 3D supramolecular frameworks constructed from 1D zig-zag chains. Complex 4 features a 3D tetra-nodal (3,4,4,5)-connected architecture containing 1D μ-COO bridged chains with (5(2)·6(2)·7.9)(5(2)·6(4)·7(3)·8)2(5(2)·6)2(6(3)·7(2)·9) topology. Complex 5 shows a 3D penta-nodal (3,4,4,6,6)-connected net containing 1D μ-OH/μ-COO bridged chains and mononuclear Co(II) nodes with a (4(2)·6(3)·8)(4(3))2(4(4)·6(2))2(4(4)·6(6)·8(5))2(4(4)·6(7)·8(4)) topology. Variable-temperature magnetic susceptibility measurements reveal that complexes 2 and 3 show antiferromagnetic interactions between the adjacent Co(II) ions, whereas 4 is a ferromagnetic system.

摘要

通过水热条件已获得了五种新型配位聚合物,即[Mn(2,2′-联吡啶)(H₂O)₂(H₂L₁)]ₙ (1)、{[Co(btb)(H₂O)₂(H₂L₁)]·0.5H₂O}ₙ (2)、[Co(bib)(H₂O)₂(H₂L₁)]ₙ (3)、[Ni₂(bpm)(H₂O)₃(L₂)]ₙ (4) 和 {[Co₂(H₂O)₃(OH)(HL₂)]·H₂O}ₙ (5),(H₄L₁ = 1,1′:2′,1′′-三联苯-4,4′,4′′,5′-四羧酸,H₄L₂ = 1,1′:2′,1′′-三联苯-3,3′′,4′,5′-四羧酸,2,2′-联吡啶 = 2,2′-联吡啶,btb = 1,4-双(1,2,4-三唑-1-基)丁烷,bib = 1,4-双(咪唑-1-基)丁烷,bpm = 双(4-吡啶基)胺)。配合物1基于一维链展现出三维超分子框架。配合物2和3均为由一维之字形链构建而成的三维超分子框架。配合物4具有三维四节点(3,4,4,5)-连接结构,包含一维μ-COO桥连链,拓扑结构为(5(2)·6(2)·7.9)(5(2)·6(4)·7(3)·8)²(5(2)·6)²(6(3)·7(2)·9)。配合物5呈现出三维五节点(3,4,4,6,6)-连接网络,包含一维μ-OH/μ-COO桥连链和单核Co(II)节点,拓扑结构为(4(2)·6(3)·8)(4(3))²(4(4)·6(2))²(4(4)·6(6)·8(5))²(4(4)·6(7)·8(4))。变温磁化率测量表明,配合物2和3在相邻Co(II)离子之间表现出反铁磁相互作用,而4是一个铁磁体系。

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