Extended Conjugation Attenuates the Quenching of Aggregation-Induced Emitters by Photocyclization Pathways

Turley, A.T.; Saha, P.K.; Danos, A.; Bismillah, A.N.; Monkman, A.P.; Yufit, D.S.; Curchod, B.F.E.; Etherington., M.K.; McGonigal, P.R.

Abstract

Herein, we expose how the antagonistic relationship between solid-state luminescence and photocyclization of oligoaryl alkenes chromophores is modulated by the conjugation length of their alkenyl backbones. Heptaaryl cycloheptatriene molecular rotors exhibit aggregation-induced emission characteristics. We show that their emission is turned off upon breaking the conjugation of the cycloheptatriene by epoxide formation. While this modification is deleterious to photoluminescence, it enables formation of extended polycyclic frameworks by Mallory reactions. We exploit this dichotomy (i) to manipulate emission properties in a controlled manner and (ii) as a synthetic tool to link together pairs of phenyl rings in a specific sequence. This method to alter the tendency of oligoaryl alkenes to undergo photocyclization can inform the design of solid-state emitters that avoid this quenching mechanism, while also allowing selective cyclization in syntheses of polycyclic aromatic hydrocarbons.

Citation

Turley, A., Saha, P., Danos, A., Bismillah, A., Monkman, A., Yufit, D., Curchod, B., Etherington., M., & McGonigal, P. (2022). Extended Conjugation Attenuates the Quenching of Aggregation-Induced Emitters by Photocyclization Pathways. Angewandte Chemie International Edition, 61(24), Article e202202193. https://doi.org/10.1002/anie.202202193

• Journal Article Type: Article
• Acceptance Date: Mar 27, 2022
• Online Publication Date: Mar 28, 2022
• Publication Date: Jun 13, 2022
• Deposit Date: Mar 28, 2022
• Publicly Available Date: Mar 29, 2022
• Journal: Angewandte Chemie International Edition
• Print ISSN: 1433-7851
• Electronic ISSN: 1521-3773
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 61
• Issue: 24
• Article Number: e202202193
• DOI: https://doi.org/10.1002/anie.202202193
• Public URL: https://durham-repository.worktribe.com/output/1209182