A1 Journal article (refereed)
A crystalline radical cation derived from Thiele’s hydrocarbon with redox range beyond 1 V (2021)

Loh, Y. K., Vasko, P., McManus, C., Heilmann, A., Myers, W. K., & Aldridge, S. (2021). A crystalline radical cation derived from Thiele’s hydrocarbon with redox range beyond 1 V. Nature Communications, 12, Article 7052. https://doi.org/10.1038/s41467-021-27104-y

JYU authors or editors

Vasko, Petra

Publication details

All authors or editors: Loh, Ying Kai; Vasko, Petra; McManus, Caitilín; Heilmann, Andreas; Myers, William K.; Aldridge, Simon

Journal or series: Nature Communications

eISSN: 2041-1723

Publication year: 2021

Volume: 12

Article number: 7052

Publisher: Nature Publishing Group

Publication country: United Kingdom

Publication language: English

DOI: https://doi.org/10.1038/s41467-021-27104-y

Publication open access: Openly available

Publication channel open access: Open Access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/78936

Abstract

Thiele’s hydrocarbon occupies a central role as an open-shell platform for new organic materials, however little is known about its redox behaviour. While recent synthetic approaches involving symmetrical carbene substitution of the CPh2 termini yield isolable neutral/dicationic analogues, the intervening radical cations are much more difficult to isolate, due to narrow compatible redox ranges (typically < 0.25 V). Here we show that a hybrid BN/carbene approach allows access to an unsymmetrical analogue of Thiele’s hydrocarbon 1, and that this strategy confers markedly enhanced stability on the radical cation. 1•+ is stable across an exceptionally wide redox range (> 1 V), permitting its isolation in crystalline form. Further single-electron oxidation affords borenium dication 12+, thereby establishing an organoboron redox system fully characterized in all three redox states. We perceive that this strategy can be extended to other transient organic radicals to widen their redox stability window and facilitate their isolation.

Keywords: hydrocarbons; free radicals; oxidation-reduction reaction; cations; chemical synthesis