Excited-State Aromatic Interactions in the Aggregation-Induced Emission of Molecular Rotors

Sturala, Jiri; Etherington, Marc K.; Bismillah, Aisha N; Higginbotham, Heather F.; Trewby, William J.; Aguilar, Juan A.; Bromley, Elizabeth H.C.; Avestro, Alyssa-Jennifer; Monkman, Andrew P.; McGonigal, Paul R.

Abstract

Small, apolar aromatic groups, such as phenyl rings, are commonly included in the structures of fluorophores in order to impart hindered intramolecular rotations, leading to desirable solid-state luminescence properties. However, they are not normally considered to take part in through-space interactions that influence the fluorescent output. Here, we report on the photoluminescence properties of a series of phenyl-ring molecular rotors bearing three, five, six, and seven phenyl groups. The fluorescent emissions from two of the rotors are found to originate, not from the localized excited state as one might ex-pect, but from unanticipated through-space aromatic dimer states. We demonstrate that these relaxed dimer states can form as a result of intra- or intermolecular interactions across a range of environments in solution and solid samples, including conditions that promote aggregation-induced emission. Computational modeling also suggests that the formation of aro-matic-dimer excited states may account for the photophysical properties of a previously reported luminogen. These results imply, therefore, that this is a general phenomenon that should be taken into account when designing and interpreting the fluorescent outputs of luminescent probes and optoelectronic devices based on fluorescent molecular rotors.

Citation

Sturala, J., Etherington, M. K., Bismillah, A. N., Higginbotham, H. F., Trewby, W. J., Aguilar, J. A., Bromley, E. H., Avestro, A.-J., Monkman, A. P., & McGonigal, P. R. (2017). Excited-State Aromatic Interactions in the Aggregation-Induced Emission of Molecular Rotors. Journal of the American Chemical Society, 139(49), 17882-17889. https://doi.org/10.1021/jacs.7b08570

• Journal Article Type: Article
• Acceptance Date: Nov 18, 2017
• Online Publication Date: Nov 18, 2017
• Publication Date: Nov 18, 2017
• Deposit Date: Nov 20, 2017
• Publicly Available Date: Nov 20, 2017
• Journal: Journal of the American Chemical Society
• Print ISSN: 0002-7863
• Electronic ISSN: 1520-5126
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 139
• Issue: 49
• Pages: 17882-17889
• DOI: https://doi.org/10.1021/jacs.7b08570
• Public URL: https://durham-repository.worktribe.com/output/1370980