TY - JOUR
T1 - Voltammetric studies on the inter-relationship between the redox chemistry of TTF, TTF+, TTF2+ and HTTF+ in acidic media
AU - Ahmed, Shaimaa Mohamed Adil Elsayed Mohamed
AU - Abdelhamid, Muhammad
AU - Nafady A Abdellah, Ayman
AU - Li, Qi
AU - Martin, Lisandra Lorraine
AU - Bond, Alan Maxwell
PY - 2015
Y1 - 2015
N2 - 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.
AB - 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.
UR - http://pubs.rsc.org.ezproxy.lib.monash.edu.au/en/content/articlepdf/2015/ra/c4ra16588h
U2 - 10.1039/c4ra16588h
DO - 10.1039/c4ra16588h
M3 - Article
SN - 2046-2069
VL - 5
SP - 18384
EP - 18390
JO - RSC Advances
JF - RSC Advances
IS - 24
ER -