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Proton transfer with a twist? Femtosecond Dynamics of 7‐(2‐pyridyl)indole in Condensed Phase and in Supersonic Jets
Author(s) -
Nosenko Y.,
WiosnaSałyga G.,
Kunitski M.,
Petkova I.,
Singh A.,
Buma W. J.,
Thummel R. P.,
Brutschy B.,
Waluk J.
Publication year - 2008
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200801350
Subject(s) - conical intersection , intramolecular force , indole test , femtosecond , proton , twist , photochemistry , supersonic speed , chemistry , excited state , molecule , pyridine , chemical physics , jet (fluid) , phase (matter) , molecular physics , atomic physics , stereochemistry , physics , laser , thermodynamics , organic chemistry , optics , geometry , mathematics , quantum mechanics
Twist‐assisted proton transfer : Excited‐state intramolecular proton transfer (ESIPT) in 7‐(2‐pyridyl)indole proceeds in a barrierless fashion and is coupled with mutual twisting of the pyridine and indole moieties. As a result, the reaction is slower in a condensed phase than in the supersonic jet‐isolated molecule (1 ps vs. about 300 fs). Ultrafast radiationless deactivation of the phototautomer occurs via a conical intersection (CI).