[Au(PH_3)]~+芳香基发光材料的光谱性质研究

用二阶微扰(MP2)法和单激发组态相互作用(CIS)法分别优化了发光材料H3PAuPh和(H3PAu)2(1,4-C6H4)2的基态和激发态的几何结构,并用含时密度泛函(TD-DFT)法计算了各发光材料的吸收光谱与磷光发射光谱。计算结果表明,H3PAuPh和(H3PAu)2(1,4-C6H4)2的磷光发射光谱均具有在Au(6p)→C(2p)的金属向配体的电荷转移(MLCT)参与下的pπ*(Ph)→pπ(Ph)跃迁的本质,并伴有Au(6p)→Au(5d)的金属中心电荷转移(MCCT)的性质。(H3PAu)2(1,4-C6H4)2是由两个H3PAuPh连接而成的。因此(H3PAu)2(1,4-C6H4)2的分子轨道也是由H3PAuPh的分子轨道组合而成的。在磷光发射中,由于轨道组合中存在pπ*或pπ的相互作用,所以(H3PAu)2(1,4-C6H4)2的最低能量磷光发射光谱谱线的波长大于H3PAuPh的相应值。

Study on spectral properties of[Au(PH3)]+luminescent material with aryl

The ground and excited-state structures of luminescent material H3PAuPh and(H3PAu)2(1,4-C6H4)2 are optimized by the Second-order Mller-Plesset perturbation(MP2) and Single excitation Configuration Interaction(CIS) methods, respectively,and the Time-Dependent Density Functional Theory(TD-DFT) method is employed to calculate the absorb spectra and phosphorescent emission spectra of H3PAuPh and(H3PAu)2(1,4-C6H4)2.The calculations show that the phosphorescences of H3PAuPh and(H3PAu)2(1,4-C6H4)2,which have the nature of p*π(Ph)→pπ(Ph) with Au effect,are attributed to Au(6p)→C(2p) charge transfer(MLCT),accompanied by Au(6p)→Au(5d) transition character(MCCT).(H3PAu)2(1,4-C6H4)2 approximately makes up of double H3PAuPh.So the molecular orbitals of(H3PAu)2(1,4-C6H4)2 can be regarded as the compounding of the molecular orbitals of H3PAuPh.The compoundings of the molecular orbitals with the reciprocities of pπ* or pπ make the lowest-energy phosphorescence energy of(H3PAu)2(1,4-C6H4)2 lower than that of H3PAuPh.