Tetrathiafulvalene redox state

Tricyclic dithiine derivatives of tetrathiafulvalene (TTF) 32 have been prepared for their increased electropolymerization potential <2000CC1005>. The effect of different tricyclic heterocycles upon the redox properties of TTF analogues was explored, and showed that the furan derivative 33 had an unusual nonplanar conformation that allowed for the attainment of higher oxidation states at relatively low oxidation potentials <2004JMC2822>. 

Muller and co-workers have prepared the first reported tetrathiafulvalene (TTF) main chain polymer which they suggest may improve metallic and redox properties of the material due to improved through-bond and through-space interactions in the solid state <1999CC1407>. They also report a simple synthesis of the polymeric material via a novel oxidative polymerisation sequence as outlined in Scheme 18. 

Due to their structural and electrochemical properties, it would appear almost obvious to combine ferrocene-containing fragments and derivatives of tetra-thiafulvalene to construct new donors for conducting CT complexes. This approach would lead to new multistage redox systems that are likely to display different solid state properties to those of their congeners. However, only very few derivatives of this type have been so far reported. What appears to be the first compound belonging to this class was prepared by Ueno et al. in 1980 [64]. Bis(ferrocenyl)tetrathiafulvalene was obtained as a transjcis isomeric mixture (6 and 7, respectively) and was shown to form 1 1 CT complexes with TCNQ and DDQ. These materials possess... 

The controlled movement in this system is controlled by the interaction among redox-active units at the redox-active tetrathiafulvalene (TTF) units. In the neutral, unperturbed state, the tetracationic cyclophane units (cyclobis(paraquat-para-phenylene), CBPQ F ) are most stable coordinated to the TTF moieties, due to electron donation and Jt-stacking interactions. However, upon oxidation of the TTF units, the CBPQT " rings become electrostatically repelled, migrating to the... 

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