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Stabilization of merocyanine by protonation, charge, and external electric fields and effects on the isomerization of spiropyran: a computational study

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Theoretical Chemistry in Belgium

Part of the book series: Highlights in Theoretical Chemistry ((HITC,volume 6))

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Abstract

Protonation, charging, and field effects on the thermal isomerization of a nitrospiropyran (SP) modified by a thiolated etheroxide chain into merocyanine (MC) are computationally studied at the DFT level. The ring opening leads to cis-MC conformers that then isomerize to the more stable trans forms. While the closed neutral spiropyran is more stable than the conjugated open forms, the merocyanine conformers are significantly stabilized by protonation, electron attachment, and ionization. For protonation on the pyran oxygen atom and electron attachment, the MC conformers are more stable than SP, and unlike for the neutral species, the ring opening is spontaneous at room temperature. Moreover, for the pyran oxygen-protonated form, the ring opening to the cis-merocyanine becomes barrierless. On the other hand, barriers comparable to the neutral remain along the thermal pathway to the cis-merocyanine conformer for ionization or electron attachment, and the barrier for isomerization is significantly higher for the N-protonated SP form. External field effects on the neutral reaction path show that ring opening to the cismerocyanine is favored when the field reduces the electron density on the pyran part, as also induced by the local field due to O protonation.

Published as part of the special collection of articles celebrating theoretical and computational chemistry in Belgium

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Authors and Affiliations

  1. Department of Chemistry, B6c, University of Liège, 4000, Liège, Belgium

    Renuka Ganesan & F. Remacle

  2. University of Liege and FNRS (Fonds National de la Recherche Scientifique), Liège, Belgium

    F. Remacle

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  1. Renuka Ganesan
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  2. F. Remacle
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Correspondence to F. Remacle .

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Editors and Affiliations

  1. Laboratory of Theoretical Chemistry, University of Namur, Namur, Belgium

    Benoît Champagne

  2. Research Group of Theoretical Chemistry and Molecular Modeling, Hasselt University, Diepenbeek, Belgium

    Michael S. Deleuze

  3. Faculteit Wetenschappen, Free University of Brussels, Brussels, Belgium

    Frank De Proft

  4. Laboratory of Crystal Engineering Inst.of Condensed Matter and Nanoscience, Catholic University of Louvain, Louvain-La-Neuve, Belgium

    Tom Leyssens

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Ganesan, R., Remacle, F. (2014). Stabilization of merocyanine by protonation, charge, and external electric fields and effects on the isomerization of spiropyran: a computational study. In: Champagne, B., Deleuze, M., De Proft, F., Leyssens, T. (eds) Theoretical Chemistry in Belgium. Highlights in Theoretical Chemistry, vol 6. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-41315-5_14

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