Determination of the local molecular structure of metal perchlorate complex from the electron paramagnetic resonance spectra for a substitution of Mn 2+ ion: a complete energy matrices study

A simple theoretical method is introduced for studying the local molecular structure of the (MnO 6 ) 10– coordination complex. By diagonalizing the complete energy matrices of the electron–electron repulsion, the ligand field and the spin–orbit coupling for a d 5 configuration ion in a trigonal ligand field, the local distortion structure of the (MnO 6 ) 10– coordination complex for Mn 2+ ions in A–PCC:Mn 2+ (PCC = {[(CH 3 ) 2 N] 2 OPOPO[N(CH 3 ) 2 ] 2 }(ClO 4 ) 2 , A = Mg, Zn) complex systems is investigated. Both the second‐order zero‐field splitting parameter b 2 0 and the fourth‐order zero‐field splitting parameter b 4 0 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 Mn 2+ ions in Mg–PCC:Mn 2+ and R = 2.20 Å, θ = 56.52° for Mn 2+ ions in Zn–PCC:Mn 2+ complex systems are determined, respectively. It is found that the theoretical calculation results of the EPR spectra for Mn 2+ ions in A–PCC:Mn 2+ complex systems are in good agreement with the experimental values. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)