Coumarin Dimer Is an Effective Photomechanochemical AND Gate for Small-Molecule Release.

He, Xiaojun, Tian, Yancong, O'Neill, Robert T ORCID: 0000-0002-4348-7635, Xu, Yuanze, Lin, Yangju ORCID: 0000-0001-6378-7179, Weng, Wengui ORCID: 0000-0003-3144-3181 and Boulatov, Roman ORCID: 0000-0002-7601-4279 (2023) Coumarin Dimer Is an Effective Photomechanochemical AND Gate for Small-Molecule Release. Journal of the American Chemical Society, 145 (42). pp. 23214-23226.

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Official URL: http://dx.doi.org/10.1021/jacs.3c07883

Abstract

Stimulus-responsive gating of chemical reactions is of considerable practical and conceptual interest. For example, photocleavable protective groups and gating mechanophores allow the kinetics of purely thermally activated reactions to be controlled optically or by mechanical load by inducing the release of small-molecule reactants. Such release only in response to a sequential application of both stimuli (photomechanochemical gating) has not been demonstrated despite its unique expected benefits. Here, we describe computational and experimental evidence that coumarin dimers are highly promising moieties for realizing photomechanochemical control of small-molecule release. Such dimers are transparent and photochemically inert at wavelengths >300 nm but can be made to dissociate rapidly under tensile force. The resulting coumarins are mechanochemically and thermally stable, but rapidly release their payload upon irradiation. Our DFT calculations reveal that both strain-free and mechanochemical kinetics of dimer dissociation are highly tunable over an unusually broad range of rates by simple substitution. In head-to-head dimers, the phenyl groups act as molecular levers to allow systematic and predictable variation in the force sensitivity of the dissociation barriers by choice of the pulling axis. As a proof-of-concept, we synthesized and characterized the reactivity of one such dimer for photomechanochemically controlled release of aniline and its application for controlling bulk gelation.

Item Type:	Article
Uncontrolled Keywords:	Bioengineering
Divisions:	Faculty of Science and Engineering > School of Physical Sciences
Depositing User:	Symplectic Admin
Date Deposited:	17 Oct 2023 15:39
Last Modified:	14 Mar 2024 20:03
DOI:	10.1021/jacs.3c07883
Open Access URL:	https://doi.org/10.1021/jacs.3c07883
Related URLs:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3173836