Fluorinated Azobenzenes in UiO‐66: Unveiling Unprecedented Photoswitching Stability and Efficiency in Azobenzene‐Based Switch@MOF Systems

Heidi Annemarie Schwartz, Markus Rödl, Kira Küssner
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Abstract

Understanding the interactions between hosts and guests in two‐component systems remains a formidable challenge due to the diverse array of adjusting factors at play. Particularly intriguing within the realm of two‐component systems are those incorporating a photoswitchable molecule within a porous metal‐organic framework (MOF) host. In such configurations, the non‐covalently attached guest molecule undergoes distinct physicochemical changes influenced by factors like guest structure, guest density, and the shape of the MOF pores. In this study, fluorinated azobenzenes (Fx‐AZB) were introduced into the rigid UiO‐66 host, and the resulting optical properties were examined with a focus on the degree of fluorination. The photoisomers of all examined compounds exhibited remarkable stability under repetitive light exposure, showing no signs of fatigue. Moreover, both photoisomers remained stable at room temperature, defying the typical T‐type photochromism associated with azobenzenes. Most notably, all fluorinated azobenzene derivatives displayed nearly complete photoswitching upon exposure to visible light within the UiO‐66 MOF host. This positions these composite materials as leaders in the realm of azobenzene‐based switch@MOF systems.
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UiO-66 中的氟化偶氮苯:揭示基于偶氮苯的 Switch@MOF 系统中前所未有的光开关稳定性和效率
由于起作用的调整因素多种多样,了解双组分系统中主客体之间的相互作用仍然是一项艰巨的挑战。在双组分系统领域,尤其引人关注的是在多孔金属有机框架(MOF)主体内加入光开关分子的双组分系统。在这种配置中,非共价连接的客体分子会受到客体结构、客体密度和 MOF 孔形状等因素的影响,发生明显的物理化学变化。本研究将氟化偶氮苯(Fx-AZB)引入刚性 UiO-66 宿主,并以氟化程度为重点考察了由此产生的光学特性。所有受检化合物的光异构体在重复光照射下都表现出显著的稳定性,没有疲劳迹象。此外,这两种光异构体在室温下也保持稳定,与偶氮苯典型的 T 型光致变色不同。最值得注意的是,所有含氟偶氮苯衍生物在 UiO-66 MOF 宿主内暴露于可见光时,都显示出几乎完全的光开关。这使得这些复合材料成为基于偶氮苯的开关@MOF 系统领域的佼佼者。
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