铁磁性双核吲哚铜配合物的理论研究

发布时间：2018-12-13 09:32

【摘要】：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.
[Abstract]:Density functional theory (DFT) combined with symmetric breakage state method (DFT-BS) was used to study the binuclear indole-copper complex [Cu2L (AZ) (DMSO)] (L = dimethylimide trianion) with bismethylamine Schiff base as ligand. The product is derived from 1-phenyl-3-methyl-4-formylpyrazole and 1-diamine-2-propanol. The effects of different density functional methods and groups on the coupling constants of copper ligand exchange were discussed by comparing the experimental data with AZ=7- azaindole anion. The results show that the calculated results of four mixed density functional methods (B3PW91B3LPPnB3P86 and PBE) and three kinds of single density functional (BPW91,BLYP and BP86) have the same symbol as the experimental values 106cm-1. However, the results obtained by using a single density functional are close to the experimental values. The coupling constant Jab obtained by both the mixed density functional and the single density functional calculation is highly dependent on the basis set, and the calculated results at the BLYP/LANL2DZ level are in the best agreement with the experimental data. The results show that there are spin delocalization and spin polarization effects in ferromagnetic complexes [Cu2L (AZ) (DMSO)].
【作者单位】：牡丹江师范学院化学化工学院;
【基金】：黑龙江省高等学校青年学术骨干支持计划资助项目(1254G061) 牡丹江师范学院“优秀青年骨干教师培训计划”资助项目(MQP201403);牡丹江师范学院教学改革重点建设项目(17-XJH19002) 黑龙江省教育厅备案项目(1352MSYYB003) 大学生创新创业资助项目(201610233007,201710233004)
【分类号】：O641.4

【相似文献】