Electrochemical Studies of the Formation Mechanism of (cation)_<i>x</i>[Ni(dmit)₂ Conductive Compounds and of their Non-Integer Oxidation State

Abstract

Abstract The mechanism of electrocrystallization of (cation) x [Ni(dmit)2 (cation = NHMe+ 3, NMe+ 4) conductive compounds is studied under non-stationary conditions by cyclic voltammetry using ultramicroelectrodes at high potential-scan rates. It is shown that the formation of non-integer oxidation state compounds proceeds through one-electron transfers combined with chemical reaction between [Ni(dmit)2 − and [Ni(dmit)2 0 electrogenerated species exhibiting integer charges. The non-integer oxidation state in (cation) x [Ni(dmit)2 compounds (cation = NBu+ 4, AsPh+ 4, NH2Me+ 2, NH3Me+), measured by the non-integer value of x, is determined under stationary conditions by use of the carbon paste electrode at very low potential-scan rates.