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Chapter Open for the Excited-State Intramolecular Thiol Proton Transfer in the Room-Temperature Solution

  • Chun-Hsiang Wang
    Chun-Hsiang Wang
    Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan (R.O.C.)
  • Zong-Ying Liu
    Zong-Ying Liu
    Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan (R.O.C.)
  • Chun-Hao Huang
    Chun-Hao Huang
    Department of Chemistry, National Taiwan Normal University, Taipei 11677, Taiwan (R.O.C.)
  • Chao-Tsen Chen*
    Chao-Tsen Chen
    Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan (R.O.C.)
    *Email: [email protected]
  • Fan-Yi Meng
    Fan-Yi Meng
    Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan (R.O.C.)
    More by Fan-Yi Meng
  • Yu-Chan Liao
    Yu-Chan Liao
    Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan (R.O.C.)
    More by Yu-Chan Liao
  • Yi-Hung Liu
    Yi-Hung Liu
    Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan (R.O.C.)
    More by Yi-Hung Liu
  • Chao-Che Chang
    Chao-Che Chang
    Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan (R.O.C.)
  • Elise Y. Li*
    Elise Y. Li
    Department of Chemistry, National Taiwan Normal University, Taipei 11677, Taiwan (R.O.C.)
    *Email: [email protected]
    More by Elise Y. Li
  • , and 
  • Pi-Tai Chou*
    Pi-Tai Chou
    Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan (R.O.C.)
    *Email: [email protected]
    More by Pi-Tai Chou
Cite this: J. Am. Chem. Soc. 2021, 143, 32, 12715–12724
Publication Date (Web):August 6, 2021
https://doi.org/10.1021/jacs.1c05602
Copyright © 2021 American Chemical Society

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    Abstract

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    We report here, for the first time, the experimental observation on the excited-state intramolecular proton transfer (ESIPT) reaction of the thiol proton in room-temperature solution. This phenomenon is demonstrated by a derivative of 3-thiolflavone (3TF), namely, 2-(4-(diethylamino)phenyl)-3-mercapto-4H-chromen-4-one (3NTF), which possesses an —S—H···O═ intramolecular H-bond (denoted by the dashed line) and has an S1 absorption at 383 nm. Upon photoexcitation, 3NTF exhibits a distinctly red emission maximized at 710 nm in cyclohexane with an anomalously large Stokes shift of 12 230 cm–1. Upon methylation on the thiol group, 3MeNTF, lacking the thiol proton, exhibits a normal Stokes-shifted emission at 472 nm. These, in combination with the computational approaches, lead to the conclusion of thiol-type ESIPT unambiguously. Further time-resolved study renders an unresolvable (<180 fs) ESIPT rate for 3NTF, followed by a tautomer emission lifetime of 120 ps. In sharp contrast to 3NTF, both 3TF and 3-mercapto-2-(4-(trifluoromethyl)phenyl)-4H-chromen-4-one (3FTF) are non-emissive. Detailed computational approaches indicate that all studied thiols undergo thermally favorable ESIPT. However, once forming the proton-transferred tautomer, the lone-pair electrons on the sulfur atom brings non-negligible nπ* contribution to the S1′ state (prime indicates the proton-transferred tautomer), for which the relaxation is dominated by the non-radiative deactivation. For 3NTF, the extension of π-electron delocalization by the diethylamino electron-donating group endows the S1′ state primarily in the ππ* configuration, exhibiting the prominent tautomer emission. The results open a new chapter in the field of ESIPT, covering the non-canonical sulfur intramolecular H-bond and its associated ESIPT at ambient temperature.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.1c05602.

    • Discussions of experimental procedures, synthetic methods, photophysical properties, possibility of the radical emission, and computational results, figures of NMR spectra, IR spectra, X-ray crystallographic structures, computed ground-state geometries, absorption and emission spectra, transient absorption spectrum, transient spectral profile, kinetic traces, calculated molecular orbitals, and calculated various energy levels, and tables of calculated excitation energies, time-resolved data, and theoretical absorption and luminescence data (PDF)

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    CCDC 20849992085000 and 2085002 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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