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Geometry of Structurally Non-Rigid Pyridinium Cations in an Excited State

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Abstract

Quantum-chemical calculations of phenyl-substituted pyridinium cations established the formation of two non-rigid equilibrium structures in a singlet excited S1 state. These two structures are characterized by a significant torsion of the methyl group and flattened geometry of the phenyl rings relative to the plane of the heteroaromatic ring, as well as sp3 hybridization of a nitrogen atom. Structural features of the S1 equilibrium structures and their deviation from the pyridinium cation geometry in the ground state explain the experimentally detected abnormally large Stokes shift.

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Acknowledgements

Our sincere thanks to Prof. Dr. Wolfgant Rettig for his lifetime professional support, kind mentorship and help. Thank you, Wolfgang, for being the best teacher and scientific advisor.

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  1. Institute of Chemistry, Humboldt University of Berlin, Brook-Taylor-Str. 2, 12489, Berlin, Germany

    Vladimir Kharlanov

  2. Leo Piccard 40/7, 8471039, Be’er-Sheva, Israel

    Vladislav Papper

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  1. Vladimir Kharlanov
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  2. Vladislav Papper
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Correspondence to Vladislav Papper.

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This manuscript is dedicated to a memory of a most brilliant physicist, a passionate educator, a well-respected colleague and a great friend Dr. Vladimir Kharlanov.

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Kharlanov, V., Papper, V. Geometry of Structurally Non-Rigid Pyridinium Cations in an Excited State. J Fluoresc 30, 1189–1195 (2020). https://doi.org/10.1007/s10895-020-02588-x

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