Pressure- and Temperature-Induced Valence Tautomeric Interconversion in ao-Dioxolene Adduct of a Cobalt-Tetraazamacrocycle Complex

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Abstract
An electronic switch at the molecular level has been realized by using a class of ionic compounds of the formula [Co(L)(diox)]Y (L=tetraazamacrocyclic ligand, Y=mononegative anion). Such compounds undergo temperature- and pressure-induced intramolecular one-electron transfer equilibria. The transition temperature of interconversion varies with the nature of the counterions Y (Y=PF6, BPh4, I). Surprisingly the effect of the anion on the transition temperature is not only governed by its volume but also by its coulombic interaction.