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 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

Preview

PDF - Published Version Available under License Creative Commons Attribution. Download (1MB) | Preview

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:	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:	06 Jan 2024 04:44
URI:	https://orca.cardiff.ac.uk/id/eprint/136274

Citation Data

Cited 17 times in Scopus. View in Scopus. Powered By Scopus® Data

Actions (repository staff only)

Edit Item