铁磁性双核吲哚铜配合物的理论研究

Theoretical studies on a ferromagnetic dinuclear copper(Ⅱ) complex with 7-azaindolate ligands

采用密度泛函理论结合对称性破损态方法(DFT-BS),以双亚甲胺席夫碱为配体的双核吲哚铜配合物[Cu2L(AZ)(DMSO)](L=双甲亚胺三阴离子,由1-苯基-3-甲基-4-甲酰吡唑和1,3-二氨-2-丙醇衍生而成;AZ=7-氮杂吲哚阴离子)作为研究对象,通过与实验数据相比较,讨论了在不同密度泛函方法与基组对金属铜配物交换耦合常数的影响.结果表明,4种混合密度泛函方法(B3PW91,B3LYP,B3P86和PBE)及3种单一密度泛函(BPW91,BLYP和BP86)的计算结果都与实验值106cm-1有着相同的符号,但使用单一密度泛函所得到的结果与实验值比较接近.不论是混合密度泛函还是单一密度泛函计算所得到的耦合常数Jab对基组都有很大的依赖性,且BLYP/LANL2DZ水平下计算所得结果与实验数据吻合程度最好.研究表明,铁磁性配合物[Cu2L(AZ)(DMSO)]中存在着自旋离域和自旋极化效应.

In the present work,the magnetic properties of ferromagnetic complex [Cu_2L（AZ）（DMSO）]（L=trianion of bis-azomethine,derived from 1-phenyl-3-methyl-4-formylpyrazol-5-one and 1,3-diaminopropan-2-ol;AZ=anion of 7-azaindole）have been investigated on the basis of various density functional theory（DFT）with the broken symmetry（BS）approach.The computational results of the hybrid density functional theory（B3PW91,B3LYP,B3P86 and PBE）and single density functional theory（BPW91,BLYP and BP86）are well agreement with the negative sign of experimental value,the result of BLYP calculation method is closer to the experimental one.The BLYP calculation method has a large dependent on the basis set.To the dinuclear copper complex,BLYP/LANL2 DZ have a significant improvement in exchange coupling constants with the experimental data.