Nonradiative Deactivation of Excited Hemicyanines Studied with Submolecular Spatial Resolution by Time-Resolved Surface Second Harmonic Generation at Liquid−Liquid Interfaces

The excited-state dynamics of aminostilbazolium dyes is known to be dominated by nonradiative deactivation through large-amplitude motion. In order to identify the coordinate(s) responsible for this process, the excited-state lifetimes of two dialkylaminostyryl-methylpyridinium iodides have been mea...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2011-03, Vol.133 (8), p.2358-2361
Main Authors: Martin-Gassin, Gaelle, Villamaina, Diego, Vauthey, Eric
Format: Article
Language:English
Subjects:
Fluorescent Dyes - chemistry
Glycerol - chemistry
Molecular Structure
Pyridinium Compounds - chemistry
Quinolinium Compounds - chemistry
Stereoisomerism
Styrenes - chemistry
Surface Properties
Time Factors
Water - chemistry
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Summary:The excited-state dynamics of aminostilbazolium dyes is known to be dominated by nonradiative deactivation through large-amplitude motion. In order to identify the coordinate(s) responsible for this process, the excited-state lifetimes of two dialkylaminostyryl-methylpyridinium iodides have been measured at liquid−liquid interfaces using time-resolved surface second harmonic generation. We found that the decay time of the excited-states of both compounds was increasing with the viscosity of the apolar phase, consisting of n-alkanes of varying length, but was unaffected by that of the polar phase, made of water/glycerol mixtures. This indicates that the nonradiative deactivation is associated with the twist of the dialkylaniline group, which is located in the apolar part of the molecule.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja109813j