双核Au配合物激发态性质的理论研究

用二阶微扰方法和单组态相互作用方法分别计算了双核Au配合物Au2(SNHCH)2(a),Au2(SN2C4H3)2(b)和Au2(SN2C2H-C6H4)2(c)基态的几何结构,并在此基础上用含时密度泛函方法计算了它们的光谱。a,b,c所具有的芳香结构是逐渐增加的。计算结果表明:芳香结构的增加会加强Au之间的相互作用;在磷光发光过程中,各金属配合物都具有C(p)/芳香环(p)→S(p)跃迁属性(LLCT)、Au(p)→Au(d)电荷转移(MCCT)属性、C(p)/芳香环(p)→Au(d)跃迁属性(LMCT)和芳香环内部p电子跃迁属性(LLCT),但随着a、b、c所具有的芳香结构的增加,Au(p)→Au(d)的电荷转移(MCCT)逐渐减弱,C(p)/芳香环(p)→Au(d)的跃迁(LMCT)也逐渐减弱,芳香环内部p电子跃迁(LLCT)属性逐渐增强,即芳香结构会改变双核Au配合物的发光性质。

Theoretical studies on eXCited states of binuclear au complexes

The ground-and excited-state structures of Au2(SNHCH)2,Au2(SN2C4H3)2 and Au2(SN2C2H-C6H4)2 are optimized by the Second-order perturbation and Single excitation Configuration Interaction methods.The Time-Dependent Density Functional Theory method is employed to calculate the spectra of the binuclear Au complexes.The results indicate that the intramolecular Au-Au interaction is enhanced with aromatic composition increasing.The lowest-energy phosphorescences of the binary Au complexes have the nature of C(p)/aromatic nucleus(p)→S(p) charge transfer(LLCT),Au(p)→Au(d) charge transfer(MCCT),C(p)/aromatic nucleus(p)→Au(d) charge transfer(LMCT) and the intra charge transfer of aromatic nucleus(p)(LLCT).Furthermore with aromatic composition increasing,the Au(p)→Au(d) charge transfer(MCCT) and C(p)/aromatic nucleus(p)→Au(d) charge transfer(LMCT) are weak,and the intra charge transfer of aromatic nucleus(p)(ILCT) is swells,which shows that aromatic composition may change luminescent mechanism of binuclear Au complexes.