Photoswitchable Imines Drive Dynamic Covalent Systems to Nonequilibrium Steady States,Journal of the American Chemical Society

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Photoswitchable Imines Drive Dynamic Covalent Systems to Nonequilibrium Steady States
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-07-18 , DOI: 10.1021/jacs.4c03817
Jiarong Wu _{1,

2} , Jake L Greenfield _{1,

2}

Affiliation

Coupling a photochemical reaction to a thermal exchange process can drive the latter to a nonequilibrium steady state (NESS) under photoirradiation. Typically, systems use separate motifs for photoresponse and equilibrium-related processes. Here, we show that photoswitchable imines can fulfill both roles simultaneously, autonomously driving a dynamic covalent system into a NESS under continuous light irradiation. We demonstrate this using transimination reactions, where E-to-Z photoisomerism generates a more kinetically labile species. At the NESS, energy is stored both in the metastable Z-isomer of the imine and in the system’s nonequilibrium constitution; when the light is switched off, this stored energy is released as the system reverts to its equilibrium state. The system operates autonomously under continuous light irradiation and exhibits characteristics of a light-driven information ratchet. This is enabled by the dual-role of the imine linkage as both the photochromic and dynamic covalent bond. This work highlights the ability and application of these imines to drive systems to NESSs, thus offering a novel approach in the field of systems chemistry.

中文翻译：

光开关亚胺驱动动态共价系统达到非平衡稳态

将光化学反应与热交换过程耦合可以在光照射下驱动后者达到非平衡稳态（NESS）。通常，系统使用单独的基序进行光响应和平衡相关过程。在这里，我们证明光可切换亚胺可以同时履行这两个角色，在连续光照射下自动将动态共价系统驱动到 NESS 中。我们使用转亚胺化反应证明了这一点，其中E至Z光异构作用产生了动力学更不稳定的物质。在 NESS 中，能量既存储在亚胺的亚稳态Z异构体中，也存储在系统的非平衡结构中；当灯关闭时，当系统恢复到平衡状态时，所存储的能量就会被释放。该系统在连续光照射下自主运行，并表现出光驱动信息棘轮的特性。这是通过亚胺键作为光致变色键和动态共价键的双重作用实现的。这项工作突出了这些亚胺将系统驱动到 NESS 的能力和应用，从而为系统化学领域提供了一种新颖的方法。

更新日期：2024-07-18

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