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Bright-to-dark-to-bright photoisomerisation in a forked (phenylene ethynylene) dendrimer prototype and its building blocks: a new mechanistic shortcut for excitation-energy transfer?

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Abstract

Dendrimers made of oligo(phenylene ethynylene) building blocks are highly organised two-dimensional macromolecules that have raised much interest for their potential use as artificial light-harvesting antennae. Excitation-energy transfer is assumed to occur from the periphery to the core via a tree-shaped graph connecting a pair of donors on each acceptor. The received photophysical mechanism involves a converging cascade of crossings among bright electronic states foremost mediated by rigid acetylenic stretching modes. On the other hand, competition with in-plane trans-bending motions has been detected experimentally in oligomers and confirmed by computations in larger species, thus suggesting the additional involvement of dark electronic states acting as intermediates. In the present work, we show that this secondary process represents an alternative pathway that may not be detrimental and could even be viewed as a mechanistic shortcut.

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Data availability statement

The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

The authors wish to acknowledge scientific and financial support from the GDR UP network and the French Ministry of Higher Education and Research for funding the PhD thesis of GB.

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Authors and Affiliations

  1. ICGM, Univ Montpellier, CNRS, ENSCM, Montpellier, France

    G. Breuil & B. Lasorne

  2. LPCT, Univ Lorraine, CNRS, Vandoeuvre-Nancy, France

    T. Etienne

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Ultrafast Phenomena from attosecond to picosecond timescales: theory and experiments. Guest editors: Franck Lépine, Lionel Poisson.

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Breuil, G., Etienne, T. & Lasorne, B. Bright-to-dark-to-bright photoisomerisation in a forked (phenylene ethynylene) dendrimer prototype and its building blocks: a new mechanistic shortcut for excitation-energy transfer?. Eur. Phys. J. Spec. Top. 232, 2101–2115 (2023). https://doi.org/10.1140/epjs/s11734-023-00816-6

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