M(phen)3Ni(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

摘要

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),开进行了结构表征.2种离子对配合物晶体的空间群都为P21,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.%Two new bimetallic ion-pair compounds,[M(phen)3][Ni(mnt)2](phen=1,10-phenanthroline,mnt2-=maleonitriledithiolate; M=Ni2+,1; Fe2+,2),have been prepared and characterized structurally.Two ion-pair crystals,crystallizing in monoclinic space group P21,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.