Characterization of the lowest excited states of metal complexes in the near infrared-region

用傅立叶变换红外光谱仪在近红外区观察到Ru（acac）_3、Ru（dpm）_3、Ru（tfa）_3、[Ru（bpy）_3]^<3+>和[Ru（NH_3）_6]^<3+>配合物的电子吸附带。用<-1>定域轨道基组CI计算方法研究了酞菁镥二聚体自由基[Lu（Pc）_2]及其相关化合物[Lu（Nc）_2]和[Lu（Nc）（Pc）]的基态和最低激发态.通过对二聚体的半经验SCMO进行么正变换，得到了位于两个配体之一上的轨道。[Lu（Pc）_2]的最低三个带7X10^3、10X10^3和15X10^3cm^<-1>，[Lu（Nc）_2]的最低三个带6X10^3cm^、<-1>8X10^3cm^<-1>和13X10^3cm^<-1>分别归属于激发态1B_1、2E_1和3E_1。C_<4v>异二聚体的基态[Lu（Nc）（Pc）]在Nc环上比在Pc环上具有更多的空穴布居。在2A_2激发态，粒子数向Pc方向移动。

Electronic adsorption bands of Ru(III) complexes, Ru(acac)_3, Ru(dpm)_3, Ru(tfa)_3, [Ru(bpy)_3]^<3+> and [Ru(NH_3)_6]^<3+>, were observes at the near infrared region by using an FT-IR spectrometer. The bands, sppeared in the near infrared region (4000*7000cm^<-1>) are assigned to the (d,d^*) transition ^2T_2*^6A_1, and ligand field and Racah parameters are estimated based on the assignment.The ground state and the lowest excited states of lutetium phthalocyanine dimer radical [Lu(Pc)_2], and those of related compounds, [Lu(Nc)_2] and [Lu(Nc)(Pc)] are studied by CI calculation on localized orbital basis set. The orbitals, which are localized on either of two ligands, are obtained by a unitarytransformation of semiempirical SCMO's of the dimer. The lowest three band 7X10^3, 10X10^3 and 15X10^3cm^<-1> for [Lu(Pc)_2]; 6X10^3cm^<-1>, 8X10^3cm^<-1> and 13X10^3cm^<-1> for [Lu(Nc)_2] are assigned to the excited state 1B_1, 2E_1, and 3E_1, respectively. The ground state of the C_<4v> heterodimer, [Lu(Nc)(Pc)], has a population of a hole more in Nc ring than in Pc ring. The population shifts toward Pc in 2A_2 excited state.