Radical Transfer

Radical Transfer

Author: Theresa Kueckmann

An air-stable 6-oxophenalenoxyl neutral radical with a tetrathiafulvalene moiety (TTF-6OPO) exhibits spin-center transfer with intramolecular electron transfer. This dynamic phenomenon is triggered by change of solvent or temperature and is accompanied by a continuous color change.

Yasushi Morita, Osaka University, Japan, and co-workers report that intermolecular hydrogen bonding between the neutral radical and solvent molecules is at the heart of the unprecedented phenomenon. Cyclic voltammetry shows that the redox potentials of TTF-6OPO becomes more favorable for the spin-center transfer by addition of 2,2,2-trifluoroethanol (TFE) to a benzonitrile solution.

The team used temperature-dependent cyclic voltammetry in a novel low-temperature electrochemical cell to investigate the redox potential shift with decreasing temperature in CH2Cl2–TFE solvent. Calculations revealed that the energy levels of the frontier molecular orbitals involved in the spin-center transfer are lowered by the intermolecular hydrogen-bonding interaction of the neutral radical with TFE.


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