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Photochromic crown‐containing molecular switches of chemosensor activity
Author(s) -
Bren Vladimir A.,
Dubonosov Alexander D.,
Minkin Vladimir I.,
Tsukanov Alexey V.,
Gribanova Tatya.,
Shepelenko Evgenii N.,
Revinsky Yurii V.,
Rybalkin Vladimir P.
Publication year - 2007
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1264
Subject(s) - chemistry , photochromism , isomerization , crown ether , acetonitrile , alkali metal , photochemistry , thiophene , ion , molecular switch , ether , catalysis , medicinal chemistry , molecule , organic chemistry
The crown‐ether functionalized 2‐( N ‐acetyl‐ N ‐arylaminomethylene)benzo[ b ]thiophene‐3(2 H )‐ones exhibit photochromic behavior involving photoinitiated Z/E ‐isomerization around the exocyclic CC bond followed by a fast thermal N → O acetyl migration and syn → anti isomerization of the resulting kinetically stable O ‐acetyl isomers. The reverse rearrangement is an acid catalyzed reaction. The addition of alkali‐earth metal ions to solutions of N ‐acyl isomers induces negligible changes in their UV/Vis spectra, which can be significantly enhanced after irradiation and conversion to the O ‐acyl isomers. The compounds obtained may be used as sensitive photodynamic chemosensors with the ‘off‐on’ mechanism for alkali‐earth ions (Ca 2+ , Ba 2+ ). Quantum‐chemical calculations using the DFT B3LYP/LanL2DZ method predict greater affinity of these sensors to Ca 2+ ions (in the gas phase) and to Ba 2+ ions (in acetonitrile). Copyright © 2007 John Wiley & Sons, Ltd.