Proton transfer with a twist? Femtosecond Dynamics of 7-(2-pyridyl)indole in Condensed Phase and in Supersonic Jets

✍ Scribed by Y. Nosenko; G. Wiosna-Sałyga; M. Kunitski; I. Petkova; A. Singh; W. J. Buma; R. P. Thummel; B. Brutschy; J. Waluk

• Publisher: John Wiley and Sons
• Year: 2008
• Tongue: English
• Weight: 384 KB
• Volume: 47
• Category: Article
• ISSN: 0044-8249
• DOI: 10.1002/anie.200801350

✦ Synopsis

The results of spectral and photophysical studies strongly suggest that photoinduced proton transfer in 7-(2-pyridyl)indole (1) is accompanied by mutual twisting of the pyridyl and indole moieties. This conclusion is supported by the unusual finding that the photoreaction is faster in a cold, supersonicjet-isolated molecule than in solutions at room temperature, and by the ultrafast repopulation of the ground state substrate. The twisting and the presence of S 1 -S 0 conical intersection (CI) are also predicted by calculations. The phenomenon may be quite general for several classes of organic molecules with intramolecular hydrogen bonds.

Recent experimental and theoretical developments demonstrate that proton transfer-a fundamental chemical reaction-is by no means a one-dimensional process. [1] In particular, for tautomerization occurring along a hydrogen bond, coupling with modes that modulate the hydrogen bond strength may be crucial. [2] Much less explored is the possibility [*] Prof.