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

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.