Taming the Complexity of Donor-Acceptor Stenhouse Adducts: Infrared Motion Pictures of the Complete Switching Pathway
Taming the Complexity of Donor-Acceptor Stenhouse Adducts: Infrared Motion Pictures of the Complete Switching Pathway
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DOI：
10.1021/jacs.9b00341
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发表时间：
2019-05-08
影响因子：
15
通讯作者：
Buma, Wybren Jan
中科院分区：
文献类型：
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作者：
Zulfikri, Habiburrahman;Koenis, Mark A. J.;Buma, Wybren Jan
在分子水平上，可以通过外部刺激沿着多种途径主动操纵的开关是下一代响应材料系统的基础。通常使用的分子光开关的操作围绕一个关键的结构坐标。光开关的功能依赖于并可以沿着多个坐标进行处理，这将提供定制和控制其行为和性能的新方法。最近开发的施受体斯坦豪斯加合物（DASAs）是一种适用于此类应用的多功能开关，它们的光化学性质很好理解，但仅负责其整体光开关机制的一部分。其余的热交换途径至今仍是未知的。本文采用快速扫描红外吸收光谱法，在到达光吸收产生的结构后，获得在基态势能面上发生的反应的瞬态指纹图谱。光谱数据用动力学建模和量子化学计算来解释结构转换。通过这种结合实验理论的方法，我们能够揭示由光开关探索的多维基态势能面的复杂性，并利用这些知识来预测，并随后确认，DASA开关如何沿着这个势能面引导。这些结果为开发面向用户的DASA开关开辟了新天地，但也为一般新型光开关的开发提供了启示。
Switches that can be actively steered by external stimuli along multiple pathways at the molecular level are the basis for next-generation responsive material systems. The operation of commonly employed molecular photoswitches revolves around one key structural coordinate. Photoswitches with functionalities that depend on and can be addressed along multiple coordinates would offer novel means to tailor and control their behavior and performance. The recently developed donor-acceptor Stenhouse adducts (DASAs) are versatile switches suitable for such applications Their photochemistry is well understood, but is only responsible for part of their overall photoswitching mechanism. The remaining thermal switching pathways are to date unknown. Here, rapid-scan infrared absorption spectroscopy is used to obtain transient fingerprints of reactions occurring on the ground state potential energy surface after reaching structures generated through light absorption. The spectroscopic data are interpreted in terms of structural transformations using kinetic modeling and quantum chemical calculations. Through this combined experimental theoretical approach, we are able to unravel the complexity of the multidimensional ground-state potential energy surface explored by the photoswitch and use this knowledge to predict, and subsequently confirm, how DASA switches can be guided along this potential energy surface. These results break new ground for developing user-geared DASA switches but also shed light on the development of novel photoswitches in general.