Coumarin Dimer Is an Effective Photomechanochemical AND Gate for Small-Molecule Release.
Coumarin Dimer Is an Effective Photomechanochemical AND Gate for Small-Molecule Release.
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香豆素二聚体是用于小分子释放的有效光学力学化学和门。
DOI：
10.1021/jacs.3c07883
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发表时间：
2023-10-25
影响因子：
15
通讯作者：
Boulatov, Roman
中科院分区：
文献类型：
--
作者：
He, Xiaojun;Tian, Yancong;O'Neill, Robert;Xu, Yuanze;Lin, Yangju;Weng, Wengui;Boulatov, Roman
化学反应的刺激响应门控具有相当大的实际意义和概念意义。例如，可光裂解的保护基团和门控机械载体允许通过光学或机械负载通过诱导小分子反应物的释放来控制纯热活化反应的动力学。这种释放仅响应于两种刺激的顺序应用（光机械化学门控）尚未得到证实，尽管其具有独特的预期益处。在这里，我们描述的计算和实验证据表明，香豆素二聚体是非常有前途的部分实现光机械化学控制的小分子释放。这种二聚体在>300 nm的波长下是透明的和光化学惰性的，但可以在张力下快速解离。所得到的香豆素是机械化学和热稳定的，但在照射后迅速释放其有效载荷。我们的DFT计算表明，应变自由和机械化学动力学的二聚体解离是高度可调的，在一个非常广泛的范围内的速率，通过简单的取代。在头对头二聚体中，苯基基团充当分子杠杆，以通过选择牵拉轴来允许解离屏障的力灵敏度的系统和可预测的变化。作为概念验证，我们合成和表征了一种这样的二聚体的反应性，用于光机械化学控制释放苯胺及其用于控制本体凝胶化的应用。
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.
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DOI：
10.1002/anie.202207557
发表时间：
2022-09-26
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
通讯作者：
--
影响因子：
62.1
作者：
Klan, Petr;Solomek, Tomas;Bochet, Christian G.;Blanc, Aurelien;Givens, Richard;Rubina, Marina;Popik, Vladimir;Kostikov, Alexey;Wirz, Jakob
通讯作者：
Wirz, Jakob
影响因子：
15
作者：
Hermes, Matthew;Boulatov, Roman
通讯作者：
Boulatov, Roman
影响因子：
56.9
作者：
Akbulatov, Sergey;Tian, Yancong;Boulatov, Roman
通讯作者：
Boulatov, Roman
影响因子：
2.8
作者：
Buckup, T.;Dorn, J.;Motzkus, M.
通讯作者：
Motzkus, M.