氧桥联希夫碱GdNi双核配合物磁学性质理论研究

摘要

采用密度泛函理论结合对称性破损态方法,选择四类方法和不同基组对氧桥联希夫碱GdⅢNiⅡ双核配合物[Ni(HL)(H2O)(tfa) Gd(hfac)2]磁学性质进行研究.结果表明,在PW91/ TZVP(Gd为DARC2-DKH-QZVP)水平下计算的数值与实验值最吻合.分子磁轨道分析显示,分子磁轨道主要由顺磁中心Gd(1)的4f轨道、顺磁中心Ni(2)的3dxz与3dx2-y2轨道、席夫碱配体提供的桥联配位O原子和三氟乙酸根离子提供的桥联配位O原子的p轨道组成.自旋布居分析表明,Gd(1)以自旋极化为主,Ni(2)以自旋离域为主.%The magnetic coupling constant of the binuclear GdⅢNiⅡcomplex[Ni(HL)(H2O)(tfa)Gd(hfac)2]were calculated using DFT-BD by several DFT methods and basis sets.The calculated values at the PW91/TZVP(Gd/DARC2-DKH-QZVP) level showed an excellent agreement with the experimental data.The analysis of magnetic orbital showed that molecule magnetic orbitals are composed of the 4f orbitals of Gd atom the 3dx2-y2orbits and 3dxz orbitals of the Ni atom and the p orbits of O atoms with trifluoroacetate ion and Dchiff base bridged.The data of spin density indicated that the spin polarization from Gd(1)and spin delocalization from Ni(2).