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Updated: May 6, 2026

Using Cyclic Voltammetry, UV-Vis-NIR, and EPR Spectroelectrochemistry to Analyze Organic Compounds
Published on: October 18, 2018
Hydrogen-bonding effect on spin-center transfer of tetrathiafulvalene-linked 6-oxophenalenoxyl evaluated using
Shinsuke Nishida1, Kozo Fukui, Yasushi Morita
1Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043 (Japan), Fax: (+81) 6-6850-5393 http://www.chem.sci.osaka-u.ac.jp/lab/nakasuji/morita/index.html; Core Research for Evolutional Science and Technology (CREST), Japan Science and Technology Agency (JST), 5 Sanban-cho, Chiyoda-ku, Tokyo 102-0075 (Japan).
Abstract:
The stable tetrathiafulvalene (TTF)-linked 6-oxophenalenoxyl neutral radical exhibits a spin-center transfer with a continuous color change in solution caused by an intramolecular electron transfer, which is dependent on solvent and temperature. Cyclic voltammetry measurements showed that addition of 2,2,2-trifluoroethanol (TFE) to a benzonitrile solution of the neutral radical induces a redox potential shift that is favorable for the spin-center transfer. Temperature-dependent cyclic voltammetry of the neutral radical using a novel low-temperature electrochemical cell demonstrated that the redox potentials change with decreasing temperature in a 199:1 CH2Cl2/TFE mixed solvent. Furthermore, theoretical calculation revealed that the energy levels of the frontier molecular orbitals involved in the spin-center transfer are lowered by the hydrogen-bonding interaction of TFE with the neutral radical. These results indicate that the hydrogen-bonding effect is a key factor for the occurrence of the spin-center transfer of TTF-linked 6-oxophenalenoxyl.
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