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

Jiawang Zhou, Ljiljana Stojanović, Andrey A. Berezin, Tommaso Battisti, Abigail Gill, Benson M. Kariuki, Davide Bonifazi, Rachel Crespo-Otero, Michael R. Wasielewski, Yi Lin Wu

Research output: Contribution to journalArticlepeer-review

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 a 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. This journal is

Original languageEnglish
Pages (from-to)767-773
Number of pages7
JournalChemical Science
Volume12
Issue number2
DOIs
Publication statusPublished - Jan 14 2021

ASJC Scopus subject areas

  • Chemistry(all)

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