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A crystalline radical cation derived from Thiele's hydrocarbon with redox range beyond 1 V

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.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1038/s41467-021-27104-y

Authors


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Role:
Author
ORCID:
0000-0003-4202-6869
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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Inorganic Chemistry
Role:
Author
ORCID:
0000-0001-5935-9112


Publisher:
Springer Nature
Journal:
Nature Communications More from this journal
Volume:
12
Article number:
7052
Place of publication:
England
Publication date:
2021-12-03
Acceptance date:
2021-11-03
DOI:
EISSN:
2041-1723
Pmid:
34862371


Language:
English
Keywords:
Pubs id:
1222381
Local pid:
pubs:1222381
Deposit date:
2022-01-11

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