The role of atropisomers on the photo-reactivity and fatigue of diarylethene-based metal–organic frameworks. (1st October 2015) - Walton, Ian M.
Abstract : Stabilization of unfavorable rotational isomers within the nanoporous crystalline matrix reduces the useful lifetime of this photo-switchable material. Abstract : Photo-responsive metal–organic frameworks (MOFs) are one example of light controlled smart materials for use in advanced sensors, data storage, actuators and molecular switches. Herein we show the design, synthesis and characterization of a photo-responsive linker that is subsequently reacted to yield MOF single crystals. The photo-responsive properties of the resultingUBMOF-2 arise from the photo-induced cyclization of the diarylethene moiety designed into the linker. Computational modeling to assess the relative energies of linker atropisomers reveals a large energetic barrier preventing facile interconversion between key species. The role of this barrier on the observed photo-induced fatigue provides useful insight into the development of advanced photo-responsive nanoporous materials.