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Lookup NU author(s): Sara Waly, Dr Joshua Karlsson, Dr Paul Waddell, Professor Andrew Benniston, Emeritus Professor Anthony Harriman
This is the authors' accepted manuscript of an article that has been published in its final definitive form by American Chemical Society, 2022.
For re-use rights please refer to the publisher's terms and conditions.
© 2022 American Chemical Society. A boron dipyrromethene (BODIPY) derivative bearing a cis-proline residue at the meso-position crystallizes in the form of platelets with strong (i.e., φF = 0.34) red fluorescence, but the absorption and emission spectra differ markedly from those for dilute solutions. A key building block for the crystal is a pseudo-dimer where hydrogen bonding aligns the proline groups and separates the terminal chromophores by ca. 25 Å. Comparison with a covalently linked bichromophore suggests that one-dimensional (1D) excitonic coupling between the terminals is too small to perturb the optical properties. However, accretion of the pseudo-dimer forms narrow channels possessing a high density of chromophores. The resultant absorption spectrum exhibits strong excitonic splitting, which can be explained quantitatively using the extended dipole approach and allowing for coupling between ca. 30 BODIPY units. Fluorescence, which decays with a lifetime of 2.2 ns, is assigned to a delocalized and (slightly) super-radiant BODIPY dimer situated at the interface and populated via electronic energy transfer from the interior.
Author(s): Waly SM, Karlsson JKG, Waddell PG, Benniston AC, Harriman A
Publication type: Article
Publication status: Published
Journal: The Journal of Physical Chemistry Part A
Year: 2022
Volume: 126
Issue: 9
Pages: 1530–1541
Print publication date: 10/03/2022
Online publication date: 01/03/2022
Acceptance date: 15/02/2022
Date deposited: 11/04/2022
ISSN (print): 1089-5639
ISSN (electronic): 1520-5215
Publisher: American Chemical Society
URL: https://doi.org/10.1021/acs.jpca.2c00035
DOI: 10.1021/acs.jpca.2c00035
ePrints DOI: 10.57711/ss8m-wy32
PubMed id: 35230124
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