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Polymerization of tetrazine-substituted diacetylenes as aggregates in suspension

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Abstract

Polydiacetylenes (PDAs) are conjugated polymers that have been widely exploited for their chromogenic and fluorogenic transitions upon exposure to external stimuli and biomolecules of interest. Herein, we propose a comparative study of the polymerization dynamics of two diacetylene derivatives, TzDA1 and TzDA2, in the form of aggregates in suspension prepared by reprecipitation method from organic solvents in water, varying the diacetylene concentration and solvent proportions, and sonication in water, varying the time and temperature. Both derivatives bear a tetrazine fluorophore, which serves both to increase the fluorescence quantum yield of the system and to track the polymerization by fluorescence quenching exclusively by the blue-PDA, and differ by the chain termination. It was shown that adding a butyl ester function in TzDA2 to a simple urethane (TzDA1) influences the polymerizability and kinetics of polymerization of the aggregates in suspension. In addition, we showed that also the preparation method and preparation conditions do have an influence on the polymerization dynamics, suggesting that a careful study of these properties should be carried out before investigating the applications of such objects.

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Acknowledgements

This project has received funding from the H2020-EU.1.1. research and innovation programme(s)–ERC-2016-STG under grant agreement No 715757.

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Authors and Affiliations

  1. Université Paris-Saclay, ENS Paris-Saclay, CNRS, PPSM, 91190, Gif-Sur-Yvette, France

    Luca Polacchi, Arnaud Brosseau, Adrien Smith, Rémi Métivier & Clémence Allain

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  1. Luca Polacchi
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  2. Arnaud Brosseau
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  3. Adrien Smith
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Contributions

Conceptualization: LP, AB, RM and CA (equal); data curation: LP (lead), AB (supporting), and AS (supporting); investigation: LP (lead) and AS (supporting); methodology: LP (lead), AB, RM and CA (supporting); project administration: LP (lead) and AB (supporting); resources: AB, RM and CA (equal); software: RM, (lead) and AB (equal); supervision: CA and RM (equal); validation: LP (lead), AB, RM and CA (equal); visualization: LP; writing—original draft: LP; writing—review and editing: CA, RM and AB (supporting).

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Correspondence to Rémi Métivier or Clémence Allain.

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Polacchi, L., Brosseau, A., Smith, A. et al. Polymerization of tetrazine-substituted diacetylenes as aggregates in suspension. Photochem Photobiol Sci 22, 2121–2132 (2023). https://doi.org/10.1007/s43630-023-00434-0

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