摘要
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。
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.
出处
《光学技术》
CAS
CSCD
北大核心
2008年第S1期106-108,111,共4页
Optical Technique
基金
国家自然科学基金资助项目(50672132
60778034)
教育部科学技术研究重点资助项目(107020)
关键词
Au配合物
激发态
磷光
芳香结构
Au complex
excited state
phosphorescence
aromatic composition
