摘要
基于密度泛函理论结合对称性破损态（DFT-BS）方法,运用不同的密度泛函和基组对反铁磁性EO叠氮铜双核配合物[Cu2（dmpe）2（μ1,1-N3）2（CH3COO）]＋的磁性质进行研究.结果显示,杂化泛函计算的结果与实验数据非常吻合,能够准确描述反铁磁性EO叠氮铜双核配合物的磁性质.磁轨道分析表明,配合物中存在3个磁通道（2个叠氮桥、1个羧酸桥）,磁通道中N原子、O原子与顺磁中心二价铜离子间都存在pd轨道重叠,对体系反铁磁性耦合相互作用都有贡献.从自旋布居分布角度来看,该配合物中顺磁中心间主要是自旋离域作用.配合物中羧酸桥传递强反铁磁性相互作用,使得顺磁中心间磁轨道的重叠增加,体系的反铁磁性相互作用增强.
The magnetic properties of the antiferromagnetic complex [Cu2（dmpe）2（μ（1,1）-N3）2（CH3COO）]＋were studied using DFT-BS by several DFT methods and basis sets.The calculated magnetic coupling constants using the hybrid density functional theory show an excellent agreement with the experimental antiferromagnetic data,and accurately describe the magnetic properties of antiferromagnetic azido-Cu（Ⅱ）binuclear complexes.The results of magnetic orbitals show that the three coupling paths（double azidoes and carboxylate）in the complex and that there is overlap between the porbits of the N atoms and the O atoms and the dorbits of Cu atoms.All these factors contribute to the antiferromagnetic coupling of the title complex.The analysis of the spin density shows that the spin delocalization effects are predominant for the ligand atoms directly coordinated to the CuⅡcations.The carboxylate bridges in the complex transfer strong antiferromagnetic interactions.The overlap integral between the magnetic orbits increases the antiferromagnetic coupling of the complex.
作者
罗树常
李宏媛
郑鹏飞
孙小媛
刘红
刘翔宇
李佐
LUO Shu-chang;LI Hong-yuan;ZHENG Peng-fei;SUN Xiao-yuan;LIU Hong;LIU Xiang-yu;LI Zuo(College of Chemical Engineering,Guizhou University of Engineering Science,Bijie 551700,China;College of Chemistry and Chemical Engineering,Ningxia University,Yinchuan 750021,China;College of Science,Guizhou University of Engineering Science,Bijie 551700,China)
出处
《分子科学学报》
CAS
CSCD
北大核心
2018年第4期270-276,共7页
Journal of Molecular Science
基金
国家自然科学基金资助项目(21463020)
贵州省教育厅青年科技人才成长项目(黔教合KY字[2017]292)
贵州省教育厅自然科学研究资助项目(黔教合KY字[2015]450号)
国家级大学生创新创业训练计划项目(201710668009)
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资助项目(黔科合LH字[2015]7588号,黔科合LH字[2017]7013号)
贵州省科技厅联合基金资助项目(黔科合J字LKB[2013]19)
贵州省化学工程与技术重点支持学科资助项目
贵州省应用化学重点实验室资助项目
