Heteronuclear versus homonuclear electron transfer mechanisms in the conductivity of solid dithiolate mixtures with methylene blue or tetraethylammonium as cations

Abstract

In [M⁺]_z[Ni(mnt)₂]^z– salts the conductivity is higher with methylene blue (MB⁺) as cation than with NEt₄⁺, indicating for MB⁺ salts heteronuclear (‘charge transfer’) interaction in the electron-transfer process; by contrast, in compacted mixtures of salts with z= 1 and z= 2, the conductivity is enhanced across the 5–95% mixture region in the NEt₄⁺-containing series but not in the MB⁺, indicating homonuclear (‘intervalence’) anionic interaction in the former.