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氰根桥联大环配合物的合成、结构与磁性研究
引用本文:倪中海,张丽芳,崔爱莉,寇会忠. 氰根桥联大环配合物的合成、结构与磁性研究[J]. 中国科学B辑, 2009, 39(9): 910-917
作者姓名:倪中海  张丽芳  崔爱莉  寇会忠
作者单位:清华大学化学系;山东大学化学系;
基金项目:国家自然科学基金(批准号:50873053,20671055);;国家重点基础研究发展计划(编号:2009CB623301);;中国博士后基金(200801414)资助
摘    要:合成了三个氰根桥联的十二核大环齿轮状配合物[Cr(bpmb)(CN)2]6-[Mn(5-Brsalpn)]6·12H2O(1)、[Co(bpmb)(CN)2]6[Mn(5-Brsalpn)]6·12H20(2)和[Co(bpmb)-(CN)2]6[Mn(5-Clsalpn)]6·24H20·8CH3CN(3)(bpmb^2-=1,2-bis(pyridine·2-carboxamido)-4-methylbenzenate),表征了其晶体结构和磁性.三配合物是同晶型的,包含交替排列的锰(Ⅲ)-Schiff碱阳离子和[M(bpmb)(CN)2]-阴离子,阴阳离子单元用氰根离子连成十二核环状结构.分子环直径约2nm.配合物1呈反铁磁性,说明通过氰根桥铬(Ⅲ).锰(Ⅲ)离子间存在反铁磁相互作用.基于一维交替链模型(哈密顿算符H=-JCrMnN∑i=0Si·Si+1)导出的磁化率公式与实验数据进行拟和得到磁耦合参数JCrMn=-2.65(6)cm^-1.

关 键 词:多核配合物  单晶结构  磁性  氰根    
收稿时间:2009-01-19
修稿时间:2009-03-04

Synthesis,crystal structures and magnetic properties of cyanide-bridged macrocyclic complexes
NI ZhongHai, ZHANG LiFang, CUI AiLi , KOU HuiZhong. Synthesis,crystal structures and magnetic properties of cyanide-bridged macrocyclic complexes[J]. Science in China(Series B), 2009, 39(9): 910-917
Authors:NI ZhongHai   ZHANG LiFang   CUI AiLi & KOU HuiZhong
Affiliation:NI ZhongHai1,2 ZHANG LiFang,1 CUI AiLi1 & KOU HuiZhong1 1 Department of Chemistry,Tsinghua University,Beijing 100084,China,2 Department of Chemistry,Sh,ong University,Jinan 250100
Abstract:Three cyanide-bridged dodecanuclear macrocyclic wheel-like complexes Cr(bpmb)(CN)216[Mn(5- Brsalpn)]6.12H20 (1), [Co(bpmb)(CN)2]6[Mn(5-Brsalpn)]6 .12H20 (2) and [Co(bpmb)(CN)2]6[Mn(5-Clsalpn)]6. 24HEO.SCHaCN (3) [bpmb2- = 1,2-bis(pyridine-2-carboxamido)-4-methylbenzenate] have been synthesized and their crystal structures and magnetic properties have been investigated. The three compounds are structurally isomorphous which consist of alternating Mn(III)-Schiff base cations and [M(bpmb)(CN)2]- anions, generating cya- nide-bridged nanosized dodecanuclear macrocyclic structures with the approximate diameter of 2 nm. The study on the magnetic property of comp through the cyanide bridges. A constant of JCrMn = -2.65(6) lex 1 reveals the antiferromagnetic interaction between the Cr(Ⅲ) and Mn(Ⅲ) ions best-fit to the magnetic susceptibily of the complex leads to the magnetic coupling cm-1 on the basis of one-dimensional alternating chain model with Hamiltonian H=-JCrMnN∑i=0Si·Si+1
Keywords:polynuclear complex  crystal structure  magnetic property  cyanide  chromium  manganese  
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