溶剂对4-叠氮苯甲酸共配叠氮铜配合物磁学性质影响的理论研究  

Effects of Solvents on the Magnetic Properties of Azido-Cu(II)Complexes with 4-Azabenzoic Acid Coligands:A Theoretical Exploration

作　　者：罗树常 刘秋秋 郑鹏飞 殷俊 刘翔宇[2] Luo Shuchang;Liu Qiuqiu;Zheng Pengfei;Yin Jun;Liu Xiangyu(College of Chemical Engineering,Guizhou University of Engineering Science,Bijie,551700;College of Chemistry and Chemical Engineering,Ningxia University,Yinchuan,750021)

机构地区：[1]贵州工程应用技术学院化学工程学院,毕节551700 [2]宁夏大学化学化工学院,银川750021

出　　处：《化学通报》2020年第6期569-575,481,共8页Chemistry

基　　金：毕节市科技计划联合基金项目(毕科联合字G[2019]10号);国家自然科学基金项目(21463020);贵州省科技厅、毕节市科技局、贵州工程应用技术学院联合基金项目(黔科合LH字[2017]7013号,黔科合LH字[2015]7588号);毕节市中药材产业化工程研究中心项目(黔教合KY字[2018]009号);贵州省化学工程与技术重点支持学科项目资助。

摘　　要：基于DFT-BS方法,在不同泛函方法和基组下研究μ-1,1叠氮、4-叠氮苯甲酸、溶剂共配的叠氮铜配合物[Cu2(4-aba)3(N3)3(CH3OH)3]2-的磁学性质。结果显示,在B2PLYP/TZVP水平下计算得到顺磁中心间的磁耦合常数为33.48cm-1,与实验值33.80cm-1最吻合,可准确描述其磁学性质。该配合物的分子磁轨道主要贡献来自于顺磁中心Cu(1)、Cu(2)的3dx2-y2轨道、N-3离子的π型轨道、4-叠氮苯甲酸的π型轨道和溶剂甲醇氧原子的p轨道。在4-叠氮苯甲酸共配的叠氮铜配合物中引入共配溶剂水及醇类,随溶剂R基供电子效应的增加,反铁磁性部分对磁耦合常数的贡献减小,其磁耦合常数J值随之增大。The magnetic properties of a azido-Cu(II)complex[Cu2(4-aba)3(N3)3(CH3OH)3]2-were studied by using the DFT-BS method under different density functional methods and basis sets.The results showed that the magnetic coupling constant between paramagnetic centers calculated at the B2PLYP/TZVP level is 33.48cm-1,which agrees well with the experimental value(33.80 cm-1).Accordingly,it could describe the magnetic properties of the azido-Cu(II)complexes.The molecular magnetic orbital of the titled complex are mainly contributed by 3dx2-y2 orbitals of the paramagnetic center Cu(1)/Cu(2),πmolecular orbitals of N-3 ion and 4-azabenzoic acid and p orbital of oxygen atom in the methanol.As results,with the increasing of electrophobic effect of R-groups solvent,the contribution of antiferromagnetic interaction decreases,whereas the values of the magnetic coupling constant increases.

关 键 词：叠氮铜配合物 溶剂 取代苯甲酸 磁耦合常数 DFT-BS 

分 类 号：O641.4[理学—物理化学]