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Organic room-temperature phosphorescence from halogen-bonded organic frameworks: hidden electronic effects in rigidified chromophores

Zhou, Jiawang, Stojanovic, Ljiljana, Berezin, Andrey A., Battisti, Tommaso, Gill, Abigail, Kariuki, Benson, Bonifazi, Davide, Crespo-Otero, Rachel, Wasielewski, Michael R. and Wu, Yi-Lin 2020. Organic room-temperature phosphorescence from halogen-bonded organic frameworks: hidden electronic effects in rigidified chromophores. Chemical Science 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: Published Online
Status: In Press
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: 26 Nov 2020 00:00
URI: http://orca-mwe.cf.ac.uk/id/eprint/136274

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