Electron-gain and -loss centres in irradiated potassium tetracyanocuprate(I)

Abstract

Exposure of K₃[Cu(CN)₄] to ⁶⁰Co γ-rays at 77 K gives an electron-gain centre, thought to be Cu(CN)₃^3–, having a planar structure with ca. 70% of the extra electron localised in the 4p_z orbital on copper. This is compared with the centres considered to be Ag(CN)₃^3–, Zn(CN)₃^2–, Cd(CN)₃^2–, and Hg(CN)₃^2–. The electron-loss centre under-goes a series of alterations on warming, one of the species apparently being the five-co-ordinate Cu(CN)₅^3– with a d_z² ground state.