Ab initio studies on spectroscopic properties of Au(I) charge-transfer complexes

作者：Pan Qing-Jiang; Zhou Xin; Zhang Hong-Xing; Fu Hong-Gang^*

来源：Chemical Journal of Chinese Universities, 2007, 28(2): 330-333.

• Au(I) complexes
• charge transfer
• excited state
• ab initio calculations

The process of charge separation of transition metal charge-transfer complexes involves the conversion of photo-energy into electrical energy, closely related to their electronic structures. We explored the charge-transfer properties of binuclear Au(I) complexes, cis-[Au-2(SHCH2PH2)(2)](2+) ( 1), cis-[Au-2(SHCH2S)(2)] (2) and ci-[Au-2(PH2CH2S)(2)] (3), using ab initio methods. Their An(I)-Au distances in the ground states at the MP2 level are 0.2972, 0.2888 and 0.2903 nm, respectively, indicating the weak attraction between the two Au atoms. Upon excitation, those of complexes 2 and 3 are shortened by ca. 0.016 nm whereas that of complex I only elongates ca. 0.002 nm. CIS calculations predict that the triplet excited states of complexes 1-3 give rise to 383, 463 and 422 nm lowest-energy emissions, respectively. These emissions are attributable to the metal-centered (MC) transition mixed with the intramolecular charge transfer (ICT) which significantly differs from the cases in the previous studied on [An(2)(SHCH2SH)(2)](2+) trans-[Au-2 (SHCH2PH2)(2)](2+) and [Au-2(PH2CH2PH2)(2)](2+).

• 出版日期2007-2-10
• 单位黑龙江大学; 吉林大学