Abstract: | The redox behavior in acetone solution of (1,5-dithiacyclooctane 1-oxide)bis(pentaammineruthenium(II)) has been characterized, where the concept of “molecular hysteresis” is presented. Detailed thermodynamics for the complex are studied, in which intramolecular electron transfer rates for Ru3+OS/Ru2+→Ru2+SO/Ru3+ were determined as 0.12 sec?1 and 0.055 sec?1. The molecular hysteresis consists of two important factors: isomerizations for the sulfoxideruthenium complexes and the slow intramolecular electron transfer in the complex; both are examined. Isomerization rates for Ru3+S→O and Ru2+O→S determined range from 0.4 to 5000 sec?1 and from 0.7 to 16 sec?1, respectively, for Ru(NH3)5(sulfoxide)]2+/3+. A mechanism for the slow electron transfer in the complex is also presented. Features of molecular hysteresis are discussed. |