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Updated: May 8, 2026

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Electron self-exchange activation parameters of diethyl sulfide and tetrahydrothiophene
1Institut für Chemie, Martin-Luther-Universität Halle-Wittenberg, Kurt-Mothes-Str. 2, 06120 Halle/Saale, Germany.
Abstract:
Electron transfer between the title compounds and their radical cations, which were generated by photoinduced electron transfer from the sulfides to excited 2,4,6-triphenylpyrylium cations, was investigated by time-resolved measurements of chemically induced dynamic nuclear polarization (CIDNP) in acetonitrile. The strongly negative activation entropies provide evidence for an associative-dissociative electron exchange involving dimeric radical cations. Despite this mechanistic complication, the free energies of activation were found to be well reproduced by the Marcus theory of electron transfer, with the activation barrier still dominated by solvent reorganization.
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