Tailoring of solid state electrical conductivity and optical electron transfer activation on of dioxygen in solution through supramolecular charge-transfer interaction in ion pairs

摘要: Abstract Redoxactive and light-sensitive ion pair complexes of the type {A 2+ [ML 2 ] −2 }, wherein A is a bipyridinium acceptor , MNi, Pd, Pt, planar dithiolene metalate, according to their solid state structure can be divided into two classes. Class I consists compounds which contain an approximately therefore form mixed stacks slightly slipped coplanar components. II strongly twisted gives rise chain-like in only each half component adopt arrangement. While application Hush-Marcus model reveals that both classes possess same mean reorganization energy for electron transfer from dianion dication, class 1 does logarithm specific electrical conductivity increase linearly with free activation this process, as calculated charge band redox potentials. For there no similar relation. Proper selection reduction potential central metal allows tailor optical transfer-induced dioxygen solution. The primary step affords oxidized donor, − reduced acceptor, •+ reduces superoxide. latter reaction compete back-electron when more negative than −0.6V. overall proceeds case MPt, suggesting photoreactive has character.