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Lookup NU author(s): Emeritus Professor Anthony Harriman, Dr Ozgur Bozdemir
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
© 2024 The Authors. Published by American Chemical Society. Perylene monoimide diesters and the corresponding phenyl-linked bichromophores are strongly fluorescent in dilute solution with minimal triplet population after relaxation of the initial Franck-Condon state. The monomer forms nonemissive face-to-face dimers in solution, wherein illumination leads to formation of a spin-correlated, triplet pair with a yield of ca. 13% and with a time constant of 4 ± 1 ps. The triplet pair, which is localized on the aggregate, cannot separate and decays with a mean lifetime of 80 ± 10 ps. The relaxed S1 state of the weakly coupled, phenyl-linked bichromophores establishes an equilibrium with an intramolecular charge-transfer state over a hundred picoseconds or so, depending on the solvent and the geometry of the linkage. This equilibrium mixture, being dominated by the relaxed S1 state, decays on the nanosecond time scale in solution at room temperature without implication of a triplet state. Self-association occurs at higher concentration and, for the para-bridged bichromophore, leads to inefficient triplet formation in tetrahydrofuran at room temperature.
Author(s): Gultekin DD, Sen S, Elmali A, Karatay A, Kose ME, Harriman A, Bozdemir OA
Publication type: Article
Publication status: Published
Journal: Journal of Physical Chemistry A
Year: 2024
Pages: ePub ahead of Print
Online publication date: 23/10/2024
Acceptance date: 15/10/2024
Date deposited: 06/11/2024
ISSN (print): 1089-5639
ISSN (electronic): 1520-5215
Publisher: American Chemical Society
URL: https://doi.org/10.1021/acs.jpca.4c05424
DOI: 10.1021/acs.jpca.4c05424
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