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Lookup NU author(s): Dr Joshua Karlsson, Dr Ozgur Bozdemir, Emeritus Professor Anthony Harriman
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
© 2025 Wiley-VCH GmbH. A trichromophore has been synthesized comprising a perylene diimide sandwiched between two perylene monoimide diester (PMIDE) units and held in place by xanthene spacers. The DFT computed structure indicates π-stacking of the three polycycles, with a mean interplanar separation of 4.2Ă, but with the central unit displaced sideways. Phenyl groups inserted between xanthene and perylene help to rigidify the structure. Electronic interactions between perylene polycycles splits the absorption spectrum, which is dominated by transitions to the upper-lying H-state. Excimer-like emission is observed in solution at room temperature, for which the lifetime is ≈22 ns in toluene and ≈8 ns in CH2Cl2. Transient absorption spectroscopy indicates the instantaneous formation of a Franck-Condon state, which undergoes rapid vibrational cooling to populate the low-lying J-state. This species transforms over 40–60 ps into an excimer-like state wherein the exciton is delocalized over all three perylenes. A slower structural re-arrangement, complete within 1 ns, minimizes electronic interactions with one of the PMIDE units and stabilizes the resultant bipartite excimer-like state.
Author(s): Gultekin DD, Khan R, Karlsson JKG, Tkachenko NV, Acar M, Bozdemir OA, Harriman A
Publication type: Article
Publication status: Published
Journal: Chemistry - A European Journal
Year: 2025
Pages: Epub ahead of print
Online publication date: 14/04/2025
Acceptance date: 14/04/2025
Date deposited: 16/05/2025
ISSN (print): 0947-6539
ISSN (electronic): 1521-3765
Publisher: John Wiley and Sons Inc.
URL: https://doi.org/10.1002/chem.202500810
DOI: 10.1002/chem.202500810
ePrints DOI: 10.57711/kccd-5483
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