硫氰根桥联双核镍配合物磁学性质理论研究  

Theoretical Study of the Magnetic Properties of Thiocyanato-Bridged Binuclear Ni(Ⅱ)Complexes

作　　者：许俊 路绍磊 钟勇 罗树常 Xu Jun;Lu Shaolei;Zhong Yong;Luo Shuchang(College of Chemical Engineering,Guizhou University of Engineering Science,Bijie 551700,China)

机构地区：[1]贵州工程应用技术学院化学工程学院,贵州毕节551700

出　　处：《山东化工》2024年第16期57-61,共5页Shandong Chemical Industry

基　　金：新型锂离子电池材料研究与开发重点实验室(黔教技[2023]028号);贵州工程应用技术学院省级大学生创新创业训练计划项目(S202210668093,S202210668099,S202210668108)。

摘　　要：基于DFT-BS方法,对μ_(1,3)-NCS桥联双核镍配合物[Ni_(2)(L2)_(2)(μ_(1,3)-NCS)_(2)(NCS)_(2)]磁学性质进行研究,在B1P86/def2-TZVP(-f)水平下计算的J_(calc)值与实验值最接近,可用于描述其磁学性质。磁轨道分析表明,磁轨道由顺磁中心二价镍离子3d_(x_(2)-y_(2))、3d_(_(z)2)轨道和桥联配体NCS-的π型分子轨道组成,通过Ni-N-C-S-Ni通道实现其磁交换作用。同时,通过改变两个顺磁中心二价镍离子之间的距离,进一步研究了其磁构关系,发现μ_(1,3)-NCS桥联双核镍配合物磁耦合常数与Ni···Ni距离之间呈现线性相关,随Ni···Ni距离的增加,顺磁中心Ni(Ⅱ)离子的Mulliken自旋密度增大,其磁耦合常数J_(calc)逐渐减小。Based on the DFT-BS method,the magnetic properties of theμ_(1,3)-NCS bridged dinuclear Ni(Ⅱ)complex[Ni_(2)(L2)_(2)(μ_(1,3)-NCS)_(2)(NCS)_(2)]were investigated,and the J_(calc) values calculated at the B1P86/def2-TZVP(-f)level were closest to the experimental values,which can be used to characterize its magnetic properties.Magnetic orbital analysis shows that the magnetic orbitals consist of the paramagnetic center divalent nickel ion 3d_(x_(2)-y_(2))and 3d_(z)2 orbitals and theπ-type molecular orbitals of the bridging ligand,which realize their superexchange interactions through the Ni-N-C-S-Ni channels.Meanwhile,the magneto-structural correlation was further investigated by varying the distance between two paramagnetic center Ni(Ⅱ)ions,and it was found that there was a linear correlation between the magnetic coupling constants ofμ_(1,3)-NCS bridged binuclear nickel complexes and the Ni-Ni distance,and with the increase of the Ni-Ni distance,the Mulliken spin density of the paramagnetic center Ni(Ⅱ)ions increased,and its magnetic coupling constant J_(calc) gradually decreases.

关 键 词：双核镍配合物 硫氰根 磁耦合常数 DFT-BS 

分 类 号：O641[理学—物理化学]