Acta Chimica Sinica ›› 2007, Vol. 65 ›› Issue (7): 595-600. Previous Articles     Next Articles

Original Articles

双核Au(I)磷硫配合物激发态性质和金属间弱相互作用的从头算研究

潘清江1, 郭元茹2, 张红星3, 付宏刚*,1   

  1. (1黑龙江大学化学化工与材料学院 哈尔滨 150080)
    (2东北林业大学材料科学与工程学院 哈尔滨 150040)
    (3吉林大学理论化学研究所理论化学计算国家重点实验室 长春 130023)
  • 收稿日期:2006-06-26 修回日期:2006-08-28 出版日期:2007-04-14 发布日期:2007-04-14
  • 通讯作者: 付宏刚

Ab initio Study on Excited-State Properties and Weak Metal-Metal Interaction of Binuclear Au(I) Complexes with Phosphorous and/or Thio Ligands

PAN Qing-Jiang1; GUO Yuan-Ru2; ZHANG Hong-Xing3; FU Hong-Gang*,1   

  1. (1 School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080)
    (2 College of Material Science and Engineering, Northeast Forestry University, Harbin 150040)
    (3 State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023)
  • Received:2006-06-26 Revised:2006-08-28 Online:2007-04-14 Published:2007-04-14

The structures of binuclear Au(I) complexes, [Au2(SHCH2SH)2]2+(1), [Au2(SHCH2SH)- PH2CH2PH2]]2+ (2), [Au2(PH2CH2PH2)2]2+ (3), [Au2(SHCH2SH)(SCH2S)] (4), [Au2(PH2CH2PH2)(SCH2S)] (5) and [Au2(SCH2S)2]2- (6), in the ground and excited states were optimized by the MP2 and CIS methods, respectively. The calculated results showed that there exist weak attractive Au(I)-Au(I) interactions for 16 in the ground states, but those are greatly streghtened for 15 and drastically weakened for 6 in the excited states. Our calculated results agree with experimental observations. The CIS calculations reveal that with the exchange of thioether, phosphine and thiolate ligands, the transition properties of the Au(I) complexes vary regularly from MC→MMLCT→MLCT (MC: metal-centered; MMLCT: metal-metal to ligand charge transfer; MLCT: metal to ligand charge transfer).

Key words: excited state, weak metal-metal interaction, binuclear Au(I) complex, ab initio method