酚氧桥联希夫碱Gd~ⅢCu~Ⅱ双核配合物磁学性质理论研究  

The Magnetic Properties of the Phenolate-bridged Schiff Base Heterometallic Gd~ⅢCu~Ⅱ Complexes: Theoretical Studies

作　　者：黄仁义 罗树常 刘秋秋 王双凤 梅红 Huang Renyi;Luo Shuchang;Liu Qiuqiu;Wang Shuangfeng;Mei Hong(School of Chemical Engineering,Guizhou University of Engineering Science,Bijie 551700,China;The Experiment Education Model Center of the Chemistry and Chemical Engineering of Guizhou Provience,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 [2]贵州省化学化工实验教学示范中心,贵州毕节551700

出　　处：《山东化工》2018年第6期13-16,共4页Shandong Chemical Industry

基　　金：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(黔科合LH字[2015]7588号;黔科合LH字[2017]7013号);国家级大学生创新创业训练计划项目(201710668010);贵州省教育厅青年科技人才成长项目(黔教合KY字[2017]292);贵州省科技厅联合基金(黔科合J字LKB[2013]19);贵州省化学工程与技术重点支持学科(黔学位合字ZDXK[2015]32号);贵州省应用化学特色重点学科

摘　　要：采用DFT-BS方法,选择GGA、混合泛函、meta-GGA方法和不同基组对酚氧桥联席夫碱Gd~ⅢCu~Ⅱ双核配合物[Cu(valaepy)_2Gd(O_2NO)_3]磁学性质进行研究。结果表明,在B3P86/TZVP(Gd为SARC2-DKH-QZVP)水平下计算的数值与实验值最吻合。分子磁轨道分析表明,分子磁轨道主要由Gd~Ⅲ离子的4f轨道、Cu~Ⅱ离子3d_(x^2-y^2)的轨道、席夫碱中酚氧桥联配位O原子的p轨道组成。自旋布居分析表明,Gd~Ⅲ以自旋极化为主,Cu~Ⅱ以自旋离域为主。The magnetic properties of the heterometallic GdIIICuII complex[Cu(valaepy)2Gd(O 2NO)3]were studied using DFT-BS by several DFT methods(GGA,HDFT,meta-GGA)and basis sets.The calculated values at the B3LYP/TZVP(Gd/SARC2-DKH-QZVP)level showed an excellent agreement with the ferromagnetic coupling Jexp=2.47 cm-1.The analysis of magnetic orbital showed that molecule magnetic orbitals are composed of the 4f orbitals of Gd atom,3d x 2-y 2 orbitals of the Cu atom and the p orbits of O atoms with phenolate-bridged.The data of spin density indicated that the spin polarization effects over GdIII ion and spin delocalization effects over CuII ion.

关 键 词：DFT-BS 酚氧桥 席夫碱 GdIIICuII双核配合物 磁学性质 

分 类 号：O641[理学—物理化学]