Electron spin resonance studies of irradiated potassium hexacyano-cobaltate(III) in various host lattices

Abstract
E.s.r. results for γ-irradiated K3Co(CN)6 in a wide range of alkali metal halide matrices are reported. The main paramagnetic species detected at 77 K were the pentacyanocobaltate(II) ion [Co(CN5)]3–, and the ‘di-isocyanide’[Co(CN)4(NC)2]4–, but various halogen-substituted complexes were formed in low concentrations. On annealing, the ‘di-isocyanide’ complexes were lost, probably by reaction with VK centres, but the remainder were stable well above room temperature. The form of the g- and A-tensors are discussed, and it is suggested that the ‘di-isocyanide’ complex probably contains two off-axis cyanide ions twisted through relatively small angles, rather than through 180° as previously postulated.

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