Using [(Tp)Fe(CN)3]-(Tp=hydrotris(pyrazolyl)borate) as a building block, one trinuelear 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(Ⅲ) 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 Ni(Ⅱ) and Fe(Ⅲ) ions, giving a S=2 ground state. The best-fit for XM T vs T with a Hamiltonian H=-2J(Sfel·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.%采用[(Tp)Fe(CN)3]-(Tp=hydrotris(pyrazolyl)borate)与[NiL](ClO4)2(L=3,10-bis(2-bydroxyethyl)-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(Ⅱ)大环与2+[(Tp)re(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(Ⅱ)和Fe(Ⅲ)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(SFel·SNi+SFe2·SNi)对其XMT-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.
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