Density functional theory study of the magnetic properties of rare earth complexes:the magnetic coupling mechanism in Y~Ⅲ and Gd~Ⅲ complexes with nitronyl nitroxide

作     者：REN Jie1,2,WANG BingWu1 & CHEN ZhiDa1 1 Beijing National Laboratory for Molecular Sciences,State Key Laboratory of Rare Earth Materials Chemistry and Applications,College of Chemistry and Molecular Engineering,Peking University,Beijing 100871,China 2 College of Science,Hebei University of Science and Technology,Shijiazhuang 050018,China 

作者机构：Beijing National Laboratory for Molecular Sciences State Key Laboratory of Rare Earth Materials Chemistry and Applications College of Chemistry and Molecular Engineering Peking University Beijing China College of Science Hebei University of Science and Technology Shijiazhuang China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2009年第52卷第11期

页      面：1961-1968页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：Supported by the 973 Project (Grant No. 2006CB601102) the National Natural Science Foundation of China (Grant No. 20973052) 

主　　题：magnetic coupling density functional theory rare earth ion gadolinium(Ⅲ) complexes yttrium(Ⅲ) complexes 

摘      要：The magnetic coupling interactions of the nitronyl nitroxide radicals bound to diamagnetic(YⅢ) and paramagnetic(GdⅢ) rare earth ions in two model magnetic systems based on novel rare earth organic radical complexes Ln(hfac)3(NITPhOCH3)2(Ln=YⅢ 1,GdⅢ 2;hafc = hexafluoroacetylacetonate;NIT-PhOCH3 = 4 -methoxyo-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) have been investigated by density functional theory(DFT).The magnetic coupling mechanisms were also explored from the viewpoint of molecular orbital and spin density *** calculations show that the empty 4d-orbitals of YⅢ and 5d-orbitals of GdⅢ play an important role in the antiferromagnetic coupling between the two nitronyl nitroxide radical ligands,and that the ferromagnetic coupling between the GdⅢ ion and the radical magnetic centers can be attributed to the nearly complete localization of the isotropic 4f-shell and singly occupied magnetic orbital(π) of the nitronyl nitroxide.