Voltammetric studies on the inter-relationship between the redox chemistry of TTF, TTF+, TTF2+ and HTTF+ in acidic media

Shaimaa Mohamed Adil Elsayed Mohamed Ahmed, Muhammad Abdelhamid, Ayman Nafady A Abdellah, Qi Li, Lisandra Lorraine Martin, Alan Maxwell Bond

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The electrochemistry of TTF, TTF+˙, TTF2+ and HTTF+ (TTF = tetrathiafulvalene) has been studied in acetonitrile (0.1 M Bu4NPF6) solutions containing ethereal HBF4 or trifluoroacetic acid (TFA) using transient and steady-state voltammetric techniques. In the absence of acid, the oxidation of TTF occurs via two, diffusion controlled, chemically and electrochemically reversible, one-electron processes with reversible formal potentials of −74 and 311 mV vs. Fc0/+ (Fc = ferrocene). The voltammetry in the presence of acid is far more complex. Voltammetric and UV-vis data reveal that the parent TTF undergoes facile protonation to yield the structurally modified HTTF+ cation in the presence of acid. In contrast, detailed analysis of the data show that electrochemically generated TTF+˙ and TTF2+ do not react with acid. The voltammetry in the presence of acid has been simulated to provide a thermodynamic and kinetic description of the acid–base chemistry coupled to electron transfer.
Original languageEnglish
Pages (from-to)18384-18390
Number of pages7
JournalRSC Advances
Volume5
Issue number24
DOIs
Publication statusPublished - 2015

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