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Femtosecond Dynamics of a Simple Merocyanine Dye:  Does Deprotonation Compete with Isomerization?

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Contribution from the Laser Dynamics Laboratory, Department of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, and National Institute for Laser Enhanced Science, Cairo University, Egypt
Cite this: J. Am. Chem. Soc. 2000, 122, 28, 6720–6726
Publication Date (Web):June 22, 2000
https://doi.org/10.1021/ja993940w
Copyright © 2000 American Chemical Society

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    Abstract

    The primary photochemistry of the trans isomer of a simple merocyanine dye of the stilbazolium betaine type 1-methyl-4-(4‘-hydroxytyryl)pyridinium betaine (Mtrans) and its conjugate acid MH+trans in aqueous solution is studied by femtosecond time-resolved pump probe spectroscopy. The measured rate of the primary photodynamics is determined to be k = 1.1 × 1012 s-1 for Mtrans at pH 10 and 0.8 × 1012 s-1 for MH+trans at pH 6. This was assigned to either conformational changes or a simple vibrational relaxation before the actual isomerization takes place. Wavelength excitation studies give support for the former assignment. These results are discussed in terms of the recent results found for the primary processes of retinal in bacteriorhodopsin. Time-resolved transient measurements show that no excited-state deprotonation of MH+trans occurs in aqueous solutions at pH 6 or pH 0, suggesting that the deprotonation occurs on a longer time scale than the picosecond time domain. This is in agreement with present theories of intermolecular proton-transfer reactions, which require solvent reorganization as well as the time of deprotonation estimated from the pKa value of this molecule in the excited state. The results of our MO calculations on the electronic structure of these two compounds could account for the fact that, while MH+trans photoisomerizes, its deprotonated form does not.

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     Georgia Institute of Technology.

    *

    In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

     National Institute for Laser Enhanced Science.

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