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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (7): 595-600. 上一篇    下一篇

研究论文

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)
  • 投稿日期:2006-06-26 修回日期:2006-08-28 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 Published:2007-04-14

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采用MP2和CIS方法分别优化双核Au(I)磷硫配合物, [Au2(SHCH2SH)2]2＋ (1), [Au2(SHCH2SH)(PH2CH2PH2)]2＋(2), [Au2(PH2CH2PH2)2]2＋ (3), [Au2(SHCH2SH)(SCH2S)] (4), [Au2(PH2CH2PH2)(SCH2S)] (5)和[Au2(SCH2S)2]2－ (6), 基态和激发态的结构. 计算结果表明基态时1～6中存在Au(I)-Au(I)弱吸引作用, 激发态时1～5的金属间相互作用明显增强而6则减弱, 这与实验研究结果一致. 单激发组态相互作用计算揭示: 磷硫配体的更替使得Au(I)配合物跃迁性质呈现MC→MMLCT→MLCT的规律性变化(MC: 金属中心; MMLCT: 金属金属到配体电荷转移; MLCT: 金属到配体电荷转移).

关键词: 激发态, 金属间弱相互作用, 双核Au(I)配合物, 从头算

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 1～6 in the ground states, but those are greatly streghtened for 1～5 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