首页> 外文期刊>Chemistry: A European journal >Making Fast Photoswitches Faster-Using Hammett Analysis to Understand the Limit of Donor-Acceptor Approaches for Faster Hemithioindigo Photoswitches
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Making Fast Photoswitches Faster-Using Hammett Analysis to Understand the Limit of Donor-Acceptor Approaches for Faster Hemithioindigo Photoswitches

机译:使用Hammett分析更快地制作快速光电开关,以了解更快的半硫靛蓝光电开关的供体-受体方法的局限性

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摘要

Hemithioindigo (HTI) photoswitches have a tremendous potential for biological and supramolecular applications due to their absorptions in the visible-light region in conjunction with ultrafast photoisomerization and high thermal bistability. Rational tailoring of the photophysical properties for a specific application is the key to exploit the full potential of HTIs as photoswitching tools. Herein we use time-resolved absorption spectroscopy and Hammett analysis to discover an unexpected principal limit to the photoisomerization rate for donor-substituted HTIs. By using stationary absorption and fluorescence measurements in combination with theoretical investigations, we offer a detailed mechanistic explanation for the observed rate limit. An alternative way of approaching and possibly even exceeding the maximum rate by multiple donor substitution is demonstrated, which give access to the fastest HTI photoswitch reported to date.
机译:半硫靛蓝(HTI)光电开关具有超快的光异构化能力和高的热双稳态性,因为它们在可见光区域具有吸收能力,因此在生物和超分子应用中具有巨大的潜力。合理地为特定应用定制光物理性质是充分利用HTI作为光开关工具的潜力的关键。本文中,我们使用时间分辨吸收光谱和Hammett分析来发现供体取代的HTI的光异构化速率的意外主要限制。通过结合使用静态吸收和荧光测量以及理论研究,我们为观察到的速率极限提供了详细的机械解释。展示了一种替代方法,可以通过多个供体替代来接近甚至超过最大速率,从而可以访问迄今为止报道的最快的HTI光电开关。

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