### 电场对杂金属串配合物[CuCuM(npa)4Cl]+(M=Pt, Pd, Ni)结构影响的理论研究

1. a 华南师范大学化学与环境学院 广州 510006;
b 教育部环境理论化学重点实验室 广州 510006;
c 广东省高校电化学储能与发电技术重点实验室 广州 510006;
d 华南师范大学 电化学储能材料与技术教育部工程研究中心 广州 510006
• 投稿日期:2012-03-23 发布日期:2012-08-03
• 通讯作者: 许旋
• 基金资助:

项目受广东省自然科学基金(No. 9151063101000037)、广东省教育部产学研项目(No. 2010B090400184)、广东省人才引进专项资金(No. C10133)、广州市科技攻关项目(No. 2011J4300063)资助.

### Theoretical Studies on Structures of Heterometal String Complexes [CuCuM(npa)4Cl]+ (M=Pt, Pd, Ni) under the Electric Field

Huang Xiaoa, Tan Yinga, Xu Xuana,b,c,d, Xu Zhiguanga,b

1. a School of Chemistry & Environment, South China Normal University, Guangzhou 510006;
b Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, Guangzhou 510006;
c Key Laboratory of Electrochemical Technology on Energy Storage and Power Generation in Guangdong Universities, Guangzhou 510006;
d Engineering Research Center of Materials and Technology for Electrochemical Energy Storage, Ministry of Education of China, South China Normal University, Guangzhou 510006
• Received:2012-03-23 Published:2012-08-03
• Supported by:

Project supported by the Natural Science Foundation of Guangdong Province, China (No. 9151063101000037), Research Project of Ministry of Education and Guangdong Province, China (No. 2010B090400184), Program of Talent Introduction of Guangdong Province, China (No. C10133), and Science and Technology Program of Guangzhou City, China (No. 2011J4300063).

The geometrical and electronic structures of heterometal string complexes [CuCuM(npa)4Cl]+ (1:M=Pt, 2:M=Pd, 3:M=Ni) were investigated theoretically by density functional theory UBP86 method with incorporating the external electric field along the metal chain in Cl→M(r) and M(r)→Cl two directions. In general, under the electric field, the spin densities of the high potential end decrease while that of the low potential end increase, and the negative charge transfers to the high potential end. When the electric field enhances, the molecular energy decreases and the dipole moment increases linearly. With the increase of the electric field, the spatial distribution of frontier orbitals changes regularly, and the energies of frontier occupied orbitals increase in the sensitive order of πnb**M(r)-N(r), which leads to the frontier occupied orbital level crossing. When the Cl→M(r) electric field is applied, the spin densities delocalize from Cu to M(r), and the positive charge transfers from Cu to M(r). Moreover, the molecular energy decreases more sensitively. Also in the Cl→M(r) electric field, the contractions of Cu-Cu and Cu-M(r) distances and the decrease of the frontier orbital energy gap are beneficial to the electron transport of the metal string complexes. However, under the M(r)→Cl electric field, the distances of Cu-Cu and Cu-M increase. The effect of M(r)→Cl electric field on the molecular energy, spin density and charge density of metal atoms are less obvious than that of Cl→M(r) electric field. When the electric field increases to some extent, the spin densities of the metal atoms remain stable values, and the changes of them are obviously asymmetric in Cl→M(r) and M(r)→Cl directions. Therefore, 1～3 may have the potential application of molecular rectifier.