The electronic structure of tris(octamethylpyrophosphoramide)manganese(II) ion. Electronic absorption, emission, and excitation spectra of Mn(OMPA)3(ClO4)2

Abstract

Single crystal absorption, emission, and excitation spectra of tris(octamethylpyrophosphoramide) - manganese(II) perchlorate are reported. Crystal field calculations for D3 symmetry support assignments of the observed bands. Interelectron repulsion, normalized spherical harmonic (NSH) trigonal potential, and spin–orbit interaction parameters are fitted, with B=670, C=3620, DQ=26 291, DSIG=−2000, DTAU=2000, and λ=60 cm−1. (The DQ, DSIG, and DTAU values correspond to the conventional crystal field parameter values of Dq=836, Dσ=−239, and Dτ=−93 cm−1.) Intensity borrowing mechanisms are discussed in light of the polarizations and splittings observed. The results are correlated with the previously reported zero field parameters.