基于[(Tp)Fe(CN)3]^-氰根桥联异金属三核配合物的合成、晶体结构及磁性(英文)  

Synthesis, Crystal Structure and Magnetic Properties of Linear Trinuclear Heterometallic Complex Based on [(Tp)Fe(CN)_3]^-

作　　者：顾金忠[1] 姜隆[2] 鲁统部[2] 谭民裕[1] 

机构地区：[1]兰州大学化学化工学院,兰州730000 [2]中山大学化学与化工学院、中山大学测试中心,广州510275

出　　处：《无机化学学报》2008年第11期1743-1747,共5页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金资助项目(No.20371051)

摘　　要：采用[(Tp)Fe(CN)3]-(Tp=hydrotris(pyrazolyl)borate)与[NiL](ClO4)2(L=3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetra-decane)反应,合成了氰根桥联的异金属三核配合物[NiL][(Tp)Fe(CN)3]2·4H2O (1),并对其结构和磁性进行了研究。该化合物晶体属于正交晶系,Pbca 空间群。配合物1中,Ni髤大环与2个[(Tp)Fe(CN)3]-通过氰根桥联,形成近似直线的三核结构。Ni原子的配位采取六配位稍畸变的八面体构型,其中大环配体上的4个N原子占据赤道平面而桥联氰根的2个N原子占据轴向位置。磁性测定表明在2-300 K的温度范围内,Ni髤和Fe髥之间通过桥联的氰根产生弱的铁磁相互作用。用哈密顿函数H=-2J(SFe1·SNi+SFe2·SNi)对其χMT-T曲线进行了拟合,得到1的朗德因子g=2.35和交换常数J=8.13 cm-1。最后,对配合物的结构与磁性的关系进行了讨论。Using [（Tp）Fe（CN）3]^- （Tp=hydrotris（pyrazolyl）borate） as a building block, one trinuclear complex [NIL] [（Tp）Fe（CN）3]2·4H2O （1） （L=3,10-bis（2-hydroxyethyl）-1,3,5,8,10,12-hexaazacyclotetradecane） was prepared and its structure and magnetic properties were studied. Complex 1 crystallizes in the orthorhombic system （Pbca）, which consists of a neutral Ni^Ⅱ Fe ^Ⅲ2 complex and four H2O molecules. In the compound 1, the macrocyclic Ni^Ⅱ is coordinated by two [（Tp）Fe（CN）3]^- moieties through cyano-bridges in trans positions, resulting in a linear trinuclear structure. The Ni^Ⅱ ion adopts a slightly distorted octahedral, with four nitrogen atoms of the macrocyclic ligand L occupying the equatorial plane and two nitrogen atoms of two cyano-bridges situated at the axial sites. Magnetic studies for complex 1 show ferromagnetic coupling between the Nin and Fe^Ⅲ ions, giving a S=2 ground state. The best-fit forχMT vs T with a Hamiltonian H=-2J（SFe1·SNi＋SFe2·SNi） leads to the parameters g=2.35, J=8.13 cm^-1 for 1. The correlations between the structures and the J values are discussed. CCDC： 675244.

关 键 词：氰根桥联 异核配合物 铁(Ⅲ)配合物 镍(Ⅱ)配合物 磁性 

分 类 号：O641.4[理学—物理化学] O614.121[理学—化学]