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Unusually slow intramolecular proton transfer dynamics of 4′-N,N-dimethylamino-3-hydroxyflavone in high n-alcohols: involvement of solvent relaxation

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Abstract

Excited state intramolecular proton transfer (ESIPT) time-constants of 4′-N, N-dimethylamino-3-hydroxyflavone (DMA3HF) in high n-alcohols - 1-butanol, 1-hexanol and 1-decanol - were measured to be 90 ps, 130 ps and 190 ps, respectively, which are unusually slow. At the same time, the solvation time-constants of the DMA3HF enol in the same set of solvents were measured as 100 ps, 150 ps and >300 ps, respectively. Thus, both the ESIPT and enol solvation time-constants in high n-alcohols increase monotonically with the alkyl chain-length of the solvent, although the increase is not strictly proportional. It appears that the H-bonding capacity of the solvent is the single major factor influencing both processes, causing them to become closely correlated. Solvation causes a drastic change in the solvent molecular configuration around the excited enol, E*, inducing the breakage of DMA3HF?solvent inter-molecular H-bonding, which in turn promotes ESIPT. Following previously reported theoretical work on ESIPT, a qualitative description of the S1 potential energy surface can be formulated, where the involvement of solvent relaxation with the ESIPT process is explained.

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Authors and Affiliations

  1. Department of Chemistry, University College of Science & Technology, University of Calcutta, 92, A.P.C. Road, Kolkata, 700 009, India

    Deborin Ghosh & Debabrata Mandal

  2. Bio-Organic Chemistry Lab, Department of Chemistry, Visva-Bharati University, Santiniketan, 731 235, India

    Shaikh Batuta & Naznin Ara Begum

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  1. Deborin Ghosh
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  2. Shaikh Batuta
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  4. Debabrata Mandal
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Correspondence to Debabrata Mandal.

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Electronic supplementary information (ESI) available. See DOI: 10.1039/c5pp00377f

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Ghosh, D., Batuta, S., Begum, N.A. et al. Unusually slow intramolecular proton transfer dynamics of 4′-N,N-dimethylamino-3-hydroxyflavone in high n-alcohols: involvement of solvent relaxation. Photochem Photobiol Sci 15, 266–277 (2016). https://doi.org/10.1039/c5pp00377f

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