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Acylhydrazone-based supramolecular assemblies undergoing a converse sol-to-gel transition on trans → cis photoisomerization
Chemical Science ( IF 7.6 ) Pub Date : 2022-06-16 , DOI: 10.1039/d2sc01657e Zhao Gao 1 , Fei Yan 1 , Lulu Shi 1 , Yifei Han 2 , Shuai Qiu 1 , Juan Zhang 1 , Feng Wang 2 , Si Wu 2 , Wei Tian 1
Chemical Science ( IF 7.6 ) Pub Date : 2022-06-16 , DOI: 10.1039/d2sc01657e Zhao Gao 1 , Fei Yan 1 , Lulu Shi 1 , Yifei Han 2 , Shuai Qiu 1 , Juan Zhang 1 , Feng Wang 2 , Si Wu 2 , Wei Tian 1
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Photoisomeric supramolecular assemblies have drawn enormous attention in recent years. Although it is a general rule that photoisomerization from a less to a more distorted isomer causes the destruction of assemblies, this photoisomerization process inducing a converse transition from irregular aggregates to regular assemblies is still a great challenge. Here, we report a converse sol-to-gel transition derived from the planar to nonplanar photoisomer conversion, which is in sharp contrast to the conventional light-induced gel collapse. A well-designed acylhydrazone-linked monomer is exploited as a photoisomer to realize the above-mentioned phase transition. In the monomer, imine is responsible for trans–cis interconversion and amide generates intermolecular hydrogen bonds enabling the photoisomerization-driven self-assembly. The counterintuitive feature of the sol-to-gel transition is ascribed to the partial trans → cis photoisomerization of acylhydrazone causing changes in stacking mode of monomers. Furthermore, the reversible phase transition is applied in the valves formed in situ in microfluidic devices, providing fascinating potential for miniature materials.
中文翻译：
基于酰腙的超分子组装体在反式→顺式光异构化过程中经历逆溶胶到凝胶的转变
近年来，光异构超分子组装体引起了极大的关注。尽管一般规则是从较少扭曲的异构体到更加扭曲的异构体的光异构化会导致组装体的破坏，但这种光异构化过程诱导从不规则聚集体到规则组装体的逆向转变仍然是一个巨大的挑战。在这里，我们报告了由平面到非平面光异构体转换衍生的逆溶胶到凝胶转变，这与传统的光诱导凝胶塌陷形成鲜明对比。利用精心设计的酰腙连接单体作为光异构体来实现上述相变。在单体中，亚胺负责反式-顺式相互转化，酰胺产生分子间氢键，从而实现光异构化驱动的自组装。溶胶到凝胶转变的反直觉特征归因于酰腙的部分反式→顺式光异构化导致单体堆积模式的变化。此外，可逆相变应用于微流体装置中原位形成的阀门，为微型材料提供了令人着迷的潜力。
更新日期：2022-06-16
中文翻译：
基于酰腙的超分子组装体在反式→顺式光异构化过程中经历逆溶胶到凝胶的转变
近年来，光异构超分子组装体引起了极大的关注。尽管一般规则是从较少扭曲的异构体到更加扭曲的异构体的光异构化会导致组装体的破坏，但这种光异构化过程诱导从不规则聚集体到规则组装体的逆向转变仍然是一个巨大的挑战。在这里，我们报告了由平面到非平面光异构体转换衍生的逆溶胶到凝胶转变，这与传统的光诱导凝胶塌陷形成鲜明对比。利用精心设计的酰腙连接单体作为光异构体来实现上述相变。在单体中，亚胺负责反式-顺式相互转化，酰胺产生分子间氢键，从而实现光异构化驱动的自组装。溶胶到凝胶转变的反直觉特征归因于酰腙的部分反式→顺式光异构化导致单体堆积模式的变化。此外，可逆相变应用于微流体装置中原位形成的阀门，为微型材料提供了令人着迷的潜力。
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