The tetrathiafulvalene dication in the gas phase: its formation and stability

Abstract

The outcome of high-energy collisions of tetrathiafulvalene radical cations, TTF˙⁺, strongly depends on the nature of the collision gas. Thus, bond cleavage of the central fulvalene bond is promoted by an inert gas, such as helium, whereas oxidation to the dication is a significant reaction channel when molecular oxygen is the collision gas. DFT calculations (B3LYP/6-311++G(2d,p)//B3LYP/6-31+G(d)) indicate that TTF²⁺ is both thermodynamically and kinetically stable with respect to dissociation into two singly charged dithiole ring fragments or a doubly charged and a neutral dithiole.