Key Laboratory of Green Chemical Media, and Reactions (Ministry of Education), Collaborative Innovation Center of Henan Province, for Green Manufacturing of Fine Chemicals, School of Chemistry and Chemical Engineering, Henan Normal University., Xinxiang, Henan, 453007, P. R. China.
School of Chemistry and Materials Engineering, Xinxiang University., Xinxiang, Henan, 453003, P. R. China.
Chemistry. 2023 May 11;29(27):e202300222. doi: 10.1002/chem.202300222. Epub 2023 Mar 27.
In recent years, light-responsive molecules have been incorporated in metal-organic frameworks (MOFs) to fabricate light-responsive intelligent devices, where reversible isomerization of the guest molecules in the nanopores is crucial. However, how to design a porous environment of MOFs to achieve a reversible isomerization remains unknown until now. In this work, donor-acceptor Stenhouse adducts (DASAs), a new kind of visible light responsive compound, were confined in the nanopores of different MOFs to study their isomerization upon visible-light irradiation/mild heating. We found that the polarity of the pore environment is the key to control the reversibility of isomerization of such guest molecules. Under the guidance of this principle, MIL-53(Al) was screened to investigate the proton conductivity and switching performance of the DASA-confined MOF. The proton conductance was up to 0.013 S cm at 80 °C and 98 % RH, and at least 30 switching cycles were achieved thanks to the Grotthuss-type mechanism and the low polarity of MIL-53(Al) pore environment.
近年来，光响应分子已被引入金属-有机骨架（MOFs）中，以制造光响应智能设备，其中客体分子在纳米孔中的可逆异构化至关重要。然而，直到现在，如何设计 MOFs 的多孔环境以实现可逆异构化仍然未知。在这项工作中，供体-受体 Stenhouse 加合物（DASAs），一种新型的可见光响应化合物，被限制在不同 MOFs 的纳米孔中，以研究它们在可见光照射/温和加热下的异构化。我们发现，孔环境的极性是控制这种客体分子异构化可逆性的关键。在这一原则的指导下，筛选了 MIL-53(Al) 以研究 DASA 限域 MOF 的质子传导和开关性能。在 80°C 和 98% RH 下，质子电导率高达 0.013 S cm，并且由于质子的协同扩散机制和 MIL-53(Al) 孔环境的低极性，至少实现了 30 次开关循环。
