Issue 34, 2022

Room temperature charge-transfer phosphorescence from organic donor–acceptor Co-crystals

Abstract

Engineering the electronic excited state manifolds of organic molecules can give rise to various functional outcomes, including ambient triplet harvesting, that has received prodigious attention in the recent past. Herein, we introduce a modular, non-covalent approach to bias the entire excited state landscape of an organic molecule using tunable ‘through-space charge-transfer’ interactions with appropriate donors. Although charge-transfer (CT) donor–acceptor complexes have been extensively explored as functional and supramolecular motifs in the realm of soft organic materials, they could not imprint their potentiality in the field of luminescent materials, and it still remains as a challenge. Thus, in the present study, we investigate the modulation of the excited state emission characteristics of a simple pyromellitic diimide derivative on complexation with appropriate donor molecules of varying electronic characteristics to demonstrate the selective harvesting of emission from its locally excited (LE) and CT singlet and triplet states. Remarkably, co-crystallization of the pyromellitic diimide with heavy-atom substituted and electron-rich aromatic donors leads to an unprecedented ambient CT phosphorescence with impressive efficiency and notable lifetime. Further, gradual minimizing of the electron-donating strength of the donors from 1,4-diiodo-2,3,5,6-tetramethylbenzene (or 1,2-diiodo-3,4,5,6-tetramethylbenzene) to 1,2-diiodo-4,5-dimethylbenzene and 1-bromo-4-iodobenzene modulates the source of ambient phosphorescence emission from the 3CT excited state to 3LE excited state. Through comprehensive spectroscopic, theoretical studies, and single-crystal analyses, we elucidate the unparalleled role of intermolecular donor–acceptor interactions to toggle between the emissive excited states and stabilize the triplet excitons. We envisage that the present study will be able to provide new and innovative dimensions to the existing molecular designs employed for triplet harvesting.

Graphical abstract: Room temperature charge-transfer phosphorescence from organic donor–acceptor Co-crystals

Supplementary files

Article information

Article type
Edge Article
Submitted
15 Jūn. 2022
Accepted
08 Aug. 2022
First published
10 Aug. 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2022,13, 10011-10019

Room temperature charge-transfer phosphorescence from organic donor–acceptor Co-crystals

S. Garain, S. N. Ansari, A. A. Kongasseri, B. Chandra Garain, S. K. Pati and S. J. George, Chem. Sci., 2022, 13, 10011 DOI: 10.1039/D2SC03343G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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