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Photoacidity as a tool to rationalize excited state intramolecular proton transfer reactivity in flavonols

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Abstract

This work presents the determination of acidic strengths at the electronic ground and excited states (pKa and pK*a) of three flavonol derivatives using electronic absorption and fluorescence emission spectroscopy. The differences of the pKa and pK*a values were successfully correlated with the molecular structures according to the substitution pattern at the flavonol structure (hydrogen, diethylamino or fluoro moieties). In order to obtain more information about the observed photoacidity of these superacids, geometry optimizations and excitation energy calculations were performed at the CAM-B3LYP/ 6-311++G(d,p) level for their neutral, protonated and deprotonated species.

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Acknowledgements

Authors are thankful for financial support and scholarships from the Brazilian agencies CNPq, CAPES, FAPESP (grant 2013/16245-2), the INEO (MCT/CNPq/FAPESP) and UNICAMP/ FAEPEX. This research was supported in part by PLGrid infrastructure.

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Authors and Affiliations

  1. Grupo de Pesquisa em Fotoquímica Orgânica Aplicada, Universidade Federai do Rio Grande do Sul, Instituto de Química, Avenida Bento Gonçalves 9500, CEP 91501-970, Porto Alegre, RS, Brazil

    Luis Gustavo Teixeira Alves Duarte, Cláudia de Ávila Braga, Fabiano da Silveira Santos & Fabiano Severo Rodembusch

  2. Chemistry Institute, University of Campinas, Rua Sérgio Buarque de Holanda s/n, Poste Code 6154, Campinas, SP, CEP 13083-970, Brazil

    Luis Gustavo Teixeira Alves Duarte, José Carlos Germino & Teresa Dib Zambón Atvars

  3. Institute of Physics, Polish Academy of Sciences, Al. Lotników 32/46, 02-668, Warsaw, Poland

    Cristina Aparecida Barboza

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  1. Luis Gustavo Teixeira Alves Duarte
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  2. José Carlos Germino
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  3. Cláudia de Ávila Braga
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  4. Cristina Aparecida Barboza
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  6. Fabiano da Silveira Santos
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  7. Fabiano Severo Rodembusch
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Correspondence to Fabiano Severo Rodembusch.

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Duarte, L.G.T.A., Germino, J.C., de Ávila Braga, C. et al. Photoacidity as a tool to rationalize excited state intramolecular proton transfer reactivity in flavonols. Photochem Photobiol Sci 17, 231–238 (2018). https://doi.org/10.1039/c7pp00334j

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