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过渡金属电荷转移配合物的电荷分离是光能转化为电能的光物理过程,与配合物的电子结构密切相关.采用从头算方法探索了双核Au(Ⅰ)配合物,cis-[Au2(SHCH2PH2)2]2+(1),cis-[Au2(SHCH2S)2](2)和cis-[Au2(PH2CH2S)2](3)的电荷转移性质.采用MP2计算得到基态的Au(Ⅰ)—Au(Ⅰ)距离分别为0.2972,0.2888和0.2903 nm,表明Au(Ⅰ)之间存在弱吸引作用;电子激发使得配合物2和3的金属间的距离缩短了约0.016 nm,而配合物1仅增长了0.002 nm.CIS方法预测配合物1~3的3A激发态分别产生383,463和422 nm最低能发射,具有金属中心(Metal-centered,MC)跃迁和分子内电荷转移(Intramolecular Charge Transfer,ICT)的混合性质.
The charge separation of transition metal charge-transfer complexes is a photophysical process that converts light energy into electrical energy, and is closely related to the electronic structure of the complex. The ab initio method has been used to investigate the interaction between binuclear Au (Ⅰ) complex, cis- [Au2 (SHCH2PH2) 2] 2+, cis- [Au2 (SHCH2S) 2] and cis- [Au2 (PH2CH2S) 2] (3) (Ⅰ) were 0.2972,0.2888 and 0.2903 nm, respectively, indicating a weak attractive attraction between Au (Ⅰ). The electron excitations shortened the intermetallic distances between complexes 2 and 3 by about 0.016 nm, while the complex 1 only increased 0.002 nm.CIS method predicts that the 3A excited states of complexes 1 ~ 3 produce the lowest emission energies of 383, 463 and 422 nm, respectively, with the metal-centered (MC) transition and the intramolecular charge transfer Mixed nature.