Abstract
A PASE (pot, step, atom, economic) synthetic approach to 5-aryl-6-arylthio-2,2′-bipyridine and 6-arylthio-2,5-diarylpyridine ligands/fluorophores has been reported via SNH in 6-aryl-5H-1,2,4-triazines/aza-Diels-Alder reaction sequence. In this article, the “1,2,4-triazine” methodology was successfully used for the synthesis of C6-thiophenol-substituted (2,2′-bi)pyridines as it is well known that thio-substituted (bi)pyridines and their aza-analogs are of wide practical interest. The photophysical properties of the obtained compounds are studied and compared with those reported earlier for 6-substituted 2,2′-bipyridines. The influence of the nature of substituents in the 6-arylthio(bi)pyridine core on the photophysical properties is discussed. It was observed that the new compounds exhibited promising photophysical properties and could be considered as potential push-pull fluorophores. In addition, they demonstrated greater Stokes shift values compared to the previously described 6-H, 6-arylamino and 6-pentafluoro-2,2′-bipyridines and higher fluorescence quantum yields values compare to pentafluorophenyl-substituted 2,2′-bipyridines. Depending on a nature of (bi)pyridine fluorophore LE (locally excited) and/or ICT (intramolecular charge transfer) state were prevailing in emission spectra.
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This work was supported by the Grants Council of the President of the Russian Federation (no. NSh-2700.2020.3), by the Russian Science Foundation (Grant # 19–73-10144) and State Contract # (0398–2019-0001 АААА-А19–119011790132-7).
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Maria I. Savchuk: Data curation, Investigation, Methodology. Dmitry S. Kopchuk: Data curation, Formal analysis, Funding acquisition, Methodology, Project administration, Supervision, Writing original draft. Olga S. Taniya: Formal analysis, Writing original draft, review, and editing. Igor L. Nikonov: Data curation, Formal analysis, Investigation, Methodology. Ilya N. Egorov: Investigation, Methodology. Sougata Santra: Conceptualization, Formal analysis, Funding acquisition, Project administration, Supervision, Writing original draft review and editing. Grigory V. Zyryanov: Conceptualization, Formal analysis, Funding acquisition, Project administration, Supervision, Writing original draft, review and editing. Oleg N. Chupakhin: Conceptualization, Project administration, Supervision. Valery N. Charushin: Conceptualization, Project administration, Supervision.
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Savchuk, M.I., Kopchuk, D.S., Taniya, O.S. et al. 5-Aryl-6-arylthio-2,2′-bipyridine and 6-Arylthio-2,5-diarylpyridine Fluorophores: Pot, Atom, Step Economic (PASE) Synthesis and Photophysical Studies. J Fluoresc 31, 1099–1111 (2021). https://doi.org/10.1007/s10895-021-02714-3
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DOI: https://doi.org/10.1007/s10895-021-02714-3