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Photochemical Generation of 9H‐Fluorenyl Radicals
Author(s) -
Dyblenko Tatiana,
Chtchemelinine Andrei,
Reiter Ryan,
Chowdhury Ruhul Q.,
Enaya Alexander,
Afifi Hanan,
Fournier Rene,
Mladenova Gabriela,
Lever Alfred Barry P.,
LeeRuff Edward
Publication year - 2014
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/php.12225
Subject(s) - radical , chemistry , photoexcitation , photochemistry , adduct , photodissociation , trifluoromethyl , solvent , hydrogen atom abstraction , polar , excitation , organic chemistry , alkyl , physics , astronomy , electrical engineering , engineering
A series of 9‐substituted fluorenols and 9,9′‐disubstituted‐9,9′‐bifluorenyls were irradiated to give products derived from fluorenyl radicals. Product distribution was solvent dependent. A TEMPO adduct was isolated from the photoexcitation of 9‐fluorenol. An unusual unsymmetrical 3,9′‐bifluorenyl was observed from the photolysis of 9‐trifluoromethylfluorenol and 9,9′‐di(trifluoromethyl)‐9,9′‐bifluorenyl in more polar or hydrogen‐bonding solvents. The electronic nature of 9‐substituted fluorenyl radicals was probed using theoretical calculations showing the dipolar character of species with electron‐deficient groups. These constitute the first examples of “doubly destabilized” radicals.