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

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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.