Stimuli-Responsive Porous Molecular Crystal with Reversible Modulation of Porosity

Responsive materials have received much attention due to modulated properties under stimuli such as light, heat, and electricity. A photoresponsive porous molecular crystal (1) has been assembled from a racemic dithienylethene-cage (L) by multiple C–F···H–C hydrogen bonds and van der Waals forces according to crystallographic investigation. Electronic absorption spectroscopy reveals reversible photochromic behaviors of the solution and film forms of enantiomeric L upon UV and visible light irradiation due to photoisomerization of dithienylethene units. X-ray photoelectron spectroscopy (XPS), in combination with NMR, discloses the quantitative photoisomerization of photochromic dithienylethene moieties. Moreover, the porosity of 1 is modulated by UV irradiation based on gas sorption data. Interestingly, heating the irradiated sample of 1 in 1,4-dioxane leads to recovered porosity due to the recovered cage molecular structure and maintained periodic frameworks.