Photophysics of trans-4-(dimethylamino)-4'-cyanostilbene and its use as a solvation probe

The Journal of Physical Chemistry. a
Sergei ArzhantsevMark Maroncelli

Abstract

Electronic structure calculations, steady-state electronic spectroscopy, and femtosecond time-resolved emission spectroscopy are used to examine the photophysics of trans-4-(dimethylamino)-4'-cyanostilbene (DCS) and its solvent dependence. Semiempirical AM1/CI calculations suggest that an anilino TICT state is a potential candidate for the emissive state of DCS in polar solvents. But observation of large and solvent-independent absorption and emission transition moments in a number of solvents (M(abs) = 6.7 +/- 0.4 D and M(em) = 7.6 +/- 0.8 D) rule out the involvement of any such state, which would have a vanishingly small transition moment. The absorption and steady-state emission spectra of DCS evolve in a systematic manner with solvent polarity, approximately as would be expected for a single, highly polar excited state. Attempts to fit the solvatochromism of DCS using standard dielectric continuum models are only partially successful when values of the solute dipole moments suggested by independent measurements are assumed. The shapes of the absorption and emission spectra of DCS change systematically with solvent polarity in a manner that is semiquantitatively reproduced using a coupled-state model of the spectroscopy. Ker...Continue Reading

References

Jul 21, 2006·The Journal of Physical Chemistry. B·Francesca IngrossoJacopo Tomasi
Jun 1, 1991·Journal of Fluorescence·J R LakowiczD Gloyna

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Citations

Aug 19, 2008·Journal of Photochemistry and Photobiology. B, Biology·Emmanuel AbrahamGediminas Jonusauskas
Oct 20, 2015·The Journal of Physical Chemistry. a·Rajib Ghosh, Dipak K Palit
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Nov 13, 2014·The Journal of Physical Chemistry. B·Jens BreffkeMark Maroncelli
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Sep 14, 2010·The Journal of Physical Chemistry. a·Xiang Li, Mark Maroncelli
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Mar 16, 2017·Physical Chemistry Chemical Physics : PCCP·Tatu KumpulainenEric Vauthey
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Nov 4, 2008·The Journal of Physical Chemistry. B·Chet SwalinaMark Maroncelli
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Jan 26, 2007·The Journal of Physical Chemistry. a·Guda Ramakrishna, Theodore Goodson

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