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Issue 45, 2019
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Tuning symmetry breaking charge separation in perylene bichromophores by conformational control

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Abstract

Understanding structure–property relationships in multichromophoric molecular architectures is a crucial step in establishing new design principles in organic electronics as well as to fully understand how nature exploits solar energy. Here, we study the excited state dynamics of three bichromophores consisting of two perylene chromophores linked to three different crown-ether backbones, using stationary and ultrafast electronic spectroscopy combined with molecular dynamics simulations. The conformational space available to the bichromophores depends on the structure and geometry of the crown-ether and can be significantly changed upon cation binding, strongly affecting the excited-state dynamics. We show that, depending on the conformational restrictions and the local environment, the nature of the excited state varies greatly, going from an excimer to a symmetry-broken charge separated state. These results can be rationalised in terms of a structure–property relationship that includes the effect of the local environment.

Graphical abstract: Tuning symmetry breaking charge separation in perylene bichromophores by conformational control

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Publication details

The article was received on 06 Aug 2019, accepted on 26 Sep 2019 and first published on 30 Sep 2019


Article type: Edge Article
DOI: 10.1039/C9SC03913A
Chem. Sci., 2019,10, 10629-10639
  • Open access: Creative Commons BY license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Tuning symmetry breaking charge separation in perylene bichromophores by conformational control

    A. Aster, G. Licari, F. Zinna, E. Brun, T. Kumpulainen, E. Tajkhorshid, J. Lacour and E. Vauthey, Chem. Sci., 2019, 10, 10629
    DOI: 10.1039/C9SC03913A

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