Determination of the local molecular structure of metal perchlorate complex from the electron paramagnetic resonance spectra for a substitution of Mn²⁺ ion: a complete energy matrices study

Abstract

A simple theoretical method is introduced for studying the local molecular structure of the (MnO6)10– coordination complex. By diagonalizing the complete energy matrices of the electron–electron repulsion, the ligand field and the spin–orbit coupling for a d5 configuration ion in a trigonal ligand field, the local distortion structure of the (MnO6)10– coordination complex for Mn2+ ions in A–PCC:Mn2+ (PCC = {[(CH3)2N]2OPOPO[N(CH3)2]2}(ClO4)2, A = Mg, Zn) complex systems is investigated. Both the second‐order zero‐field splitting parameter b20 and the fourth‐order zero‐field splitting parameter b40 are taken simultaneously in the structural investigation. From electron paramagnetic resonance (EPR) calculations, the local structure parameters R = 2.18 Å, θ = 56.38° for Mn2+ ions in Mg–PCC:Mn2+ and R = 2.20 Å, θ = 56.52° for Mn2+ ions in Zn–PCC:Mn2+ complex systems are determined, respectively. It is found that the theoretical calculation results of the EPR spectra for Mn2+ ions in A–PCC:Mn2+ complex systems are in good agreement with the experimental values. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)