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)]6·12H2O(2)和[Co(bpmb)-(CN)2]6[Mn(5-Clsalpn)]6·24H2O·8CH3CN(3)(bpmb2-=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=-JCrMn∑N i=0 si·S i+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. Three cyanide bridged twelve-ring macrocyclic gearhead complexes [Cr (bpmb) (CN) 2] 6- [Mn (5-Brsalpn)] 6 · 12H2O (1) (CN) 2] 6 [Mn (5-Brsalpn)] 6 · 12H2O (2) and [Co (bpmb) - (CN) 2] 6 [Mn (5-Clsalpn)] 6 · 24H2O · 8CH3CN bpmb2- = 1,2-bis (pyridine-2-carboxamido) -4-methylbenzenate, which is characterized by its crystal structure and magnetism.The tricompounds are isomorphous and contain alternating manganese (III) And [M (bpmb) (CN) 2] - anions, respectively. The anions and cations are linked by cyanide ions into a dodecameric ring with a diameter of about 2 nm. The complex 1 is antiferromagnetic, (Ⅲ) -Mn (Ⅲ) ions.The magnetic susceptibility formula derived from one-dimensional alternating chain model (Hamiltonian H = -JCrMnΣN i = 0 si · S i + 1) The experimental data were fitted to obtain the magnetic coupling parameter JCrMn = -2.65 (6) cm-1.