首页|硫氰根桥联双核镍配合物磁学性质理论研究

硫氰根桥联双核镍配合物磁学性质理论研究

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基于DFT-BS方法,对μ1,3-NCS桥联双核镍配合物[Ni2(L2)2(μ1,3-NCS)2(NCS)2]磁学性质进行研究,在B1P86/def2-TZVP(-f)水平下计算的Jcalc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3dx2-y2、3dz2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μ1,3-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Jcalc逐渐减小.
Theoretical Study of the Magnetic Properties of Thiocyanato-Bridged Binuclear Ni(Ⅱ)Complexes
Based on the DFT-BS method,the magnetic properties of the μ1,3-NCS bridged dinuclear Ni(Ⅱ)complex[Ni2(L2)2(μ1,3-NCS)2(NCS)2]were investigated,and the Jcalc 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 3dx2-y2and 3dz2 orbitals and the π-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 of μ1,3-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 Jcalc gradually decreases.

dinuclear Ni(Ⅱ)complexesthiocyanatomagnetic coupling constantDFT-BS

许俊、路绍磊、钟勇、罗树常

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贵州工程应用技术学院化学工程学院,贵州毕节 551700

双核镍配合物 硫氰根 磁耦合常数 DFT-BS

新型锂离子电池材料研究与开发重点实验室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

黔教技[2023]028号S202210668093S202210668099S202210668108

2024

山东化工
山东省化工研究院 山东省化工信息中心

山东化工

影响因子：0.249
ISSN：1008-021X
年,卷(期)：2024.53(16)