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Excited-state intramolecular proton transfer in 10-hydroxybenzoquinoline, 1-hydroxyanthraquinone, methyl salicylate and 4-methyl-2,6-diformyl phenol: a QM/MM–MD study

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Abstract

The reaction dynamics of excited-state intramolecular proton transfer (ESIPT) tautomerism in 10-hydroxybenzoquinoline (HBQ), 1-hydroxyanthraquinone (HAQ), methyl salicylate (MS) and 4-methyl-2,6-diformyl phenol (MFOH) has been investigated by quantum mechanics/molecular mechanics–molecular dynamics (QM/MM–MD) simulation with four different solvents H2O, CH3OH, CH2Cl2 and CHCl3. The ESIPT of HBQ proceeds 20 ± 8 fs in water and methanol solvents; whereas, for other two solvents, CH2Cl2 and CHCl3, proton transfer (PT) occurs within 62 ± 6 fs and 76 ± 6 fs, respectively. Similarly, the ESIPT of HAQ proceeds 21 ± 6 fs in H2O, 33 ± 6 fs in CH3OH, 51 ± 6 fs in CH2Cl2 and 61 ± 6 fs in CHCl3. The ESIPT of MS proceeds in 23 ± 6 fs in H2O, 38 ± 6 fs in CH3OH, 60 ± 6 fs in CH2Cl2 and 73 ± 6 fs in CHCl3. The ESIPT of MFOH proceeds 20 ± 6, 22 ± 6, 35 ± 6 and 58 ± 6 fs in H2O, CH3OH, CH2Cl2 and CHCl3 solvent, respectively. Our QM/MM–MD simulations show that the rate of PT is inversely proportional to the polarity of the solvents. In addition, intramolecular hydrogen bonding capacity between the hydroxyl oxygen (proton donor) and the benzoquinolinic nitrogen (proton acceptor) plays an important role for the ESIPT reaction.

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Acknowledgements

We are grateful to Professor Cheol Ho Choi, Kyungpook National University, for his support to use his laboratory facilities for this study.

Funding

This research did not receive any specific grant from funding agencies in the public, commercial or not-for-profit sectors.

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Authors and Affiliations

  1. Clean Energy Research Center, Korea Institute of Science and Technology, Seoul, 02792, South Korea

    Md Al Mamunur Rashid

  2. Department of Mathematical and Physical Sciences, East West University, A/2, Jahurul Islam Avenue, Jahurul Islam City, Aftabnagar, Dhaka, 1212, Bangladesh

    Thamina Acter

  3. Department of Nutrition and Food Engineering, Daffodil International University, Daffodil Smart City (DSC), Birulia, Savar, Dhaka, 1216, Bangladesh

    Nizam Uddin

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  1. Md Al Mamunur Rashid
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MAMR worked in investigation, methodology and writing—review and editing; TA helped in reviewing, validation and visualization; NU helped in conceptualization, supervision and writing—original draft.

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Correspondence to Nizam Uddin.

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Rashid, M.A., Acter, T. & Uddin, N. Excited-state intramolecular proton transfer in 10-hydroxybenzoquinoline, 1-hydroxyanthraquinone, methyl salicylate and 4-methyl-2,6-diformyl phenol: a QM/MM–MD study. Theor Chem Acc 142, 96 (2023). https://doi.org/10.1007/s00214-023-03045-1

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