ESR Studies of Electron Irradiated K3IrIII(CN)6in KCl Single Crystals. I. Ligand Hyperfine Structure in IrII(CN)5Species

摘要

Electron irradiation of the diamagnetic Ir(CN)63minus;ion in a KCl host lattice produces two paramagnetic species. ESR studies reveal that one of the species can be assigned to the pentacoordinated Ir(CN)53minus;, of approximateC4ngr;symmetry, with 5d7low spin configuration, arising from the trapping of an electron in adz2orbital followed by the loss of an axial cyanide. Ligand hyperfine structure with four equivalent and one nonequivalent nitrogens is observed and confirmed by isotopic substitution. Thegvalues and the ligand hyperfine tensors are presented and discussed. Ligandfsandfpspins densities are calculated and discussed.