Abstract
Photochromic molecules have shown much promise as molecular components of stimuli-responsive materials, but despite recent achievements in various photoresponsive materials, quantitative conversion in photochemical reactions in solids is hampered by the lack of intrinsic structural flexibility available to release stress and strain upon photochemical events. This issue remains one of the challenges in developing solid-state photoresponsive materials. Here, we report a strategy to realize photoresponsive crystalline materials showing quantitative reversible photochemical reactions upon ultraviolet and visible light irradiation by introducing structural flexibility into crystalline porous frameworks with a twofold interpenetration composed of a diarylethene-based ligand. The structural flexibility of the porous framework enables highly efficient photochemical electrocyclization in a single-crystal-to-single-crystal manner. CO2 sorption on the porous crystal at 195 K is reversibly modulated by light irradiation, and coincident X-ray powder diffraction/sorption measurements clearly demonstrate the flexible nature of the twofold interpenetrated frameworks.
Highlights
Photochromic molecules have shown much promise as molecular components of stimuliresponsive materials, but despite recent achievements in various photoresponsive materials, quantitative conversion in photochemical reactions in solids is hampered by the lack of intrinsic structural flexibility available to release stress and strain upon photochemical events
Photochemically reactive modules have been introduced on the pore surfaces as struts or in the pores of porous coordination polymers (PCPs)/metal–organic frameworks (MOFs) as guest molecules to control the porous properties by light[10,11,12,13,14,15,16], potentially leading to on-demand type materials for molecular storage, separation, and catalysis
Taking advantage of the flexible nature of the entangled framework, the porous crystal shows a quantitative and reversible isomerization upon UV and visible light irradiation, which is applicable to reversible photomodulation of its gas sorption properties
Summary
Photochromic molecules have shown much promise as molecular components of stimuliresponsive materials, but despite recent achievements in various photoresponsive materials, quantitative conversion in photochemical reactions in solids is hampered by the lack of intrinsic structural flexibility available to release stress and strain upon photochemical events. This issue remains one of the challenges in developing solid-state photoresponsive materials. We report a strategy to realize photoresponsive crystalline materials showing quantitative reversible photochemical reactions upon ultraviolet and visible light irradiation by introducing structural flexibility into crystalline porous frameworks with a twofold interpenetration composed of a diarylethene-based ligand. Taking advantage of the flexible nature of the entangled framework, the porous crystal shows a quantitative and reversible isomerization upon UV and visible light irradiation, which is applicable to reversible photomodulation of its gas sorption properties
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