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Phototransformation of anthraquinone-2-sulphonate in aqueous solution

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Abstract

Anthraquinone-2-sulphonate (AQ2S) is a triplet sensitiser that has recently been used to model the photoreactivity of chromophoric dissolved organic matter (CDOM). We show that the photolysis quantum yield of AQ2S under UVA irradiation varies from (3.4 ± 0.2) × 10−3 at μM AQ2S levels to (1.8 ± 0.1) × 10−2 at 3 mM AQ2S (μ ± σ). This trend is consistent with a combination of direct phototransformation and transformation sensitised by a photogenerated reactive species. In both cases a transient water adduct of AQ2S would be involved. Depending on the initial quinone concentration, the adduct could undergo transformation, give back ground-state AQ2S or react with it. The prevalence of the latter process at high AQ2S concentration would account for the increased values of the photolysis quantum yield. When using AQ2S as a triplet sensitiser, one should not exceed an initial concentration of 0.1 mM. Under the latter conditions the sensitised process is negligible compared to the direct photolysis, providing a simpler system to be studied, and the photolysis quantum yield is independent of the initial AQ2S concentration. This paper also shows, by adoption of density functional theory calculations, that the triplet state of AQ2S has most of the spin density localised on C=O, analogous to other photoactive quinones, which accounts for the oxidising character of the triplet state that tends to be reduced to a semiquinone radical.

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Authors and Affiliations

  1. Dipartimento di Chimica, Università degli Studi di Torino, Via Giuria 5, 10125, Torino, Italy

    Andrea Bedini, Elisa De Laurentiis, Babita Sur, Valter Maurino, Claudio Minero & Davide Vione

  2. Department of Chemical Engineering, Calcutta University, 92 Acharya P. C. Road, Kolkata, 700009, India

    Babita Sur

  3. Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000, Clermont-Ferrand, France

    Marcello Brigante & Gilles Mailhot

  4. CNRS, UMR 6296, ICCF, BP 80026, Aubière, France

    Marcello Brigante & Gilles Mailhot

  5. Centro Interdipartimentale NatRisk, Università degli Studi di Torino, Via Leonardo da Vinci 44, 10095, Grugliasco (TO), Italy

    Davide Vione

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  1. Andrea Bedini
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  2. Elisa De Laurentiis
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  3. Babita Sur
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Correspondence to Marcello Brigante or Davide Vione.

Additional information

Electronic supplementary information (ESI) available: Additional data of the DFT study of AQ2S T1, LFP transient absorption spectra. See DOI: 10.1039/c2pp25111f

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Bedini, A., De Laurentiis, E., Sur, B. et al. Phototransformation of anthraquinone-2-sulphonate in aqueous solution. Photochem Photobiol Sci 11, 1445–1453 (2012). https://doi.org/10.1039/c2pp25111f

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