通过原位固态生成螺吡喃开关构建多刺激响应性高孔隙率可切换框架

Construction of Multi-Stimuli Responsive Highly Porous Switchable Frameworks by In Situ Solid-State Generation of Spiropyran Switches.

作者信息

Sheng Jinyu, Perego Jacopo, Bracco Silvia, Czepa Włodzimierz, Danowski Wojciech, Krause Simon, Sozzani Piero, Ciesielski Artur, Comotti Angiolina, Feringa Ben L

机构信息

Stratingh Institute for Chemistry, University of Groningen, Groningen, the Netherlands. Nijenborgh 4, Groningen, AG, 9747, The Netherlands.

Department of Materials Science, University of Milano Bicocca, Milan, Italy. Via R. Cozzi 55, Milan, 20125, Italy.

出版信息

Adv Mater. 2024 Jan;36(4):e2305783. doi: 10.1002/adma.202305783. Epub 2023 Dec 3.

Abstract

Stimuli-responsive molecular systems support within permanently porous materials offer the opportunity to host dynamic functions in multifunctional smart materials. However, the construction of highly porous frameworks featuring external-stimuli responsiveness, for example by light excitation, is still in its infancy. Here a general strategy is presented to construct spiropyran-functionalized highly porous switchable aromatic frameworks by modular and high-precision anchoring of molecular hooks and an innovative in situ solid-state grafting approach. Three spiropyran-grafted frameworks bearing distinct functional groups exhibiting various stimuli-responsiveness are generated by two-step post-solid-state synthesis of a parent indole-based material. The quantitative transformation and preservation of high porosity are demonstrated by spectroscopic and gas adsorption techniques. For the first time, a highly efficient strategy is provided to construct multi-stimuli-responsive, yet structurally robust, spiropyran materials with high pore capacity which is proved essential for the reversible and quantitative isomerization in the bulk as demonstrated by solid-state NMR spectroscopy. The overall strategy allows to construct dynamic materials that undergoes reversible transformation of spiropyran to zwitterionic merocyanine, by chemical and physical stimulation, showing potential for pH active control, responsive gas uptake and release, contaminant removal, and water harvesting.

摘要

在永久性多孔材料中构建刺激响应性分子体系为多功能智能材料中承载动态功能提供了契机。然而,构建具有外部刺激响应性(例如通过光激发)的高孔隙率框架仍处于起步阶段。本文提出了一种通用策略,通过分子钩子的模块化和高精度锚定以及创新的原位固态接枝方法,构建螺吡喃功能化的高孔隙率可切换芳香框架。通过母体吲哚基材料的两步后固态合成,生成了三种带有不同官能团、表现出各种刺激响应性的螺吡喃接枝框架。光谱和气体吸附技术证明了高孔隙率的定量转化和保留。首次提供了一种高效策略,用于构建具有高孔容量的多刺激响应且结构坚固的螺吡喃材料,固态核磁共振光谱表明,这对于本体中的可逆和定量异构化至关重要。总体策略允许构建通过化学和物理刺激实现螺吡喃向两性离子部花青可逆转变的动态材料,显示出在pH活性控制、响应性气体吸收和释放、污染物去除以及水收集方面的潜力。

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