[M(phen)3][Ni(mnt)2](M2+=Ni2+，Fe2+；phen=1，10-菲咯啉，mnt2-=马来二腈二硫烯)离子对配合物的合成、晶体结构、电子光谱和磁性质

本文制备了2种新的离子对配合物M(phen)3]Ni(mnt)2](phen=1,10-菲咯啉,mnt2-=马来二腈二硫烯;M2+=Ni2+,1;Fe2+,2),并进行了结构表征。2种离子对配合物晶体的空间群都为P21/n,具有类似的晶胞参数和堆积结构。紫外可见-近红外光谱显示在近红外区域没有出现明显的吸收峰。在2到400 K的温度范围内,化合物1表现居里-外斯型的顺磁性行为,并在磁性Ni(phen)3]2+离子之间存在弱的反铁磁作用,而且在八面体配位环境下Ni2+离子自旋基态S=1。化合物2在40 K向上显示抗磁性,意味Fe(phen)3]2+离子处于低自旋态。低于40 K时,弱居里尾巴可能是由于小部分顺磁性Ni(mnt)2]-杂质导致的。

Syntheses, Crystal Structures, Electronic Spectra and Magnetic Properties for New Ion-Pair Complexes of [M(phen)3][Ni(mnt)2] (M2+=Ni2+, Fe2+; phen=1,10-phenathroline, mnt2-=maleonitriledithiolate)

Two new bimetallic ion-pair compounds, M(phen)₃]Ni(mnt)₂] (phen=1,10-phenanthroline, mnt^2-=maleonitriledithiolate; M=Ni²⁺, 1; Fe²⁺, 2), have been prepared and characterized structurally. Two ion-pair crystals, crystallizing in monoclinic space group P2₁/n, have quite similar cell parameters and packing structures, and two compounds do not show the absorption in the near-IR region. Compound 1 exhibits the Curie-Weiss-type paramagnetic behavior in the temperature range 2~400 K and the existence of weakly antiferromagnetic coupling between magnetic Ni(phen)₃]²⁺ ions and the Ni²⁺ ion in the octahedral coordination sphere has an S=1 ground state. While 2 displays the diamagnetic behavior above ~40 K with a weak Curie-Weiss type paramagnetic tail below 40 K, indicated the Fe²⁺ center in the Fe(phen)₃]²⁺ ion having a low-spin state. The weak paramagnetic behavior in the low-temperature region results from a trace amount of Ni(mnt)₂]^- species. CCDC: 860552, 1; 860551, 2.