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.
作者
罗树常
刘秋秋
郑鹏飞
殷俊
刘翔宇
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)
出处
《化学通报》
CAS
CSCD
北大核心
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。
关键词
叠氮铜配合物
溶剂
取代苯甲酸
磁耦合常数
DFT-BS
Azido-Cu(II)complexes
Solvent
Substituted benzoic acid
Magnetic coupling constant
DFT-BS
