Zhou, Jiawang, Stojanovic, Ljiljana, Berezin, Andrey A., Battisti, Tommaso, Gill, Abigail, Kariuki, Benson  ORCID: https://orcid.org/0000-0002-8658-3897, Bonifazi, Davide ORCID: https://orcid.org/0000-0001-5717-0121, Crespo-Otero, Rachel, Wasielewski, Michael R. and Wu, Yi-Lin ORCID: https://orcid.org/0000-0003-0253-1625
2021.
Organic room-temperature phosphorescence from halogen-bonded organic frameworks: hidden electronic effects in rigidified chromophores.
Chemical Science
12
(2)
, pp. 767-773.
10.1039/D0SC04646A
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Abstract
Development of purely organic materials displaying room-temperature phosphorescence (RTP) will expand the toolbox of inorganic phosphors for imaging, sensing or display applications. While molecular solids were found to suppress non-radiative energy dissipation and make the RTP process kinetically favourable, such an effect should be enhanced by the presence of multivalent directional non-covalent interactions. Here we report phosphorescence of a series of fast triplet-forming tetraethyl naphthalene-1,4,5,8-tetracarboxylates. Various numbers of bromo substituents were introduced to modulate intermolecular halogen-bonding interactions. Bright RTP with quantum yields up to 20% was observed when the molecule is surrounded by Br⋯O halogen-bonded network. Spectroscopic and computational analyses revealed that judicious heavy-atom positioning suppresses non-radiative relaxation and enhances intersystem crossing at the same time. The latter effect was found to be facilitated by the orbital angular momentum change, in addition to the conventional heavy-atom effect. Our results suggest the potential of multivalent non-covalent interactions for excited-state conformation and electronic control.
| Item Type: | Article |
|---|---|
| Date Type: | Publication |
| Status: | Published |
| Schools: | Schools > Chemistry |
| Additional Information: | This article is licensed under a Creative Commons Attribution 3.0 Unported Licence |
| Publisher: | Royal Society of Chemistry |
| ISSN: | 2041-6520 |
| Funders: | EU, EPSRC and Leverhulme Trust |
| Date of First Compliant Deposit: | 11 November 2020 |
| Date of Acceptance: | 4 November 2020 |
| Last Modified: | 17 Jul 2025 21:16 |
| URI: | https://orca.cardiff.ac.uk/id/eprint/136274 |
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