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Updated: May 22, 2025

Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds
Published on: October 18, 2018
Determination of the intervalence charge-transfer rate in mixed-valence arylamino-fluorene derivatives using EPR
Alessandro Agostini1, Mirco Zerbetto1, Davide Sartori1
1Department of Chemical Sciences, University of Padova, Via Marzolo 1, 35131 Padova, Italy.
Abstract:
Thermally activated electron-transfer processes are of interest for a variety of theoretical and technological applications. In organic mixed-valence (MV) systems, the intramolecular charge transfer between two redox centers offers valuable insights about the kinetics and energetics of electron hopping. We investigated the intramolecular charge transfer process in a series of MV organic molecules where two arylamino units are linked together by a variable length bridge. The experimental investigation is carried out by means of Electron Paramagnetic Resonance (EPR) spectroscopy on MV radical cations. The EPR spectra, recorded in a series of solvents at different temperatures, were adequately simulated using a multiple-site random jump model implemented in a software routine, providing the intramolecular charge transfer rate as the output. The dependence of the free energy of the electron transfer process on the solvent allowed us to identify a correlation between the energetic of the charge transfer and some solvent properties.
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