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Durham e-Theses
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Functionalised tetrathiafulvalenes in supramolecular chemistry

Skabara, Peter John (1994) Functionalised tetrathiafulvalenes in supramolecular chemistry. Doctoral thesis, Durham University.



Using a range of functionalised tetrathiafulvalene (TTF) derivatives, developed at Durham, the first examples of covalently linked TTF-ferrocene systems have been prepared. The redox properties of these molecules, as studied by cyclic voltammetry, provide evidence that these species are efficient π-electron donors. Highly reactive 1,3-dithiole Wittig and Wittig-Homer reagents have been used in the synthesis of complex mixed redox-active systems containing ferrocenyl units. A series of [3]- and [4]-dendralenes has also been developed from this synthetic methodology. Cyclic voltammetry shows that tri- and tetracationic states can be achieved with these systems at relatively low potentials. The potential for vinyl-TTF compounds to undergo [4+2] cycloaddition has been investigated for the first time. The peripheral C=C unit of TTF, together with the adjacent vinylic substituent, is able to act as the diene functionality in Diels-Alder reactions. Remarkably, the π-delocalisation within the TTF moieties is readily disrupted by the addition of strong dienophiles. The reactivity of lithiated TTF towards aldehydes and ketones has established an array of hydroxy-functionalised TTF, bis-TTF and TTF-ferrocene derivatives. The conducting and magnetic properties of the chloranil charge transfer salt of one of these species is also reported.

Item Type:Thesis (Doctoral)
Award:Doctor of Philosophy
Thesis Date:1994
Copyright:Copyright of this thesis is held by the author
Deposited On:14 Mar 2014 17:09

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