Engineering Photoswitching Dynamics in 3D Photochromic Metal-Organic Frameworks through Metal-Organic Polyhedron Design

Metal-organic polyhedra (MOPs) are versatile supramolecular building blocks for the design of highly porous frame-works by reticular assembly because of their diverse geometries, multiple degrees of freedom regarding functionaliza-tion, and accessible metal sites. Lipophilic functionalization is demonstrated to enable the rational assembly and crystal-lization with photoactive N-donor ligands in an aliphatic solvent to achieve multiaxially aligned photoresponsive dia-rylethene (DTE) moieties in 3D frameworks (DUT-210(M), M= Cu, Rh) featuring cooperative switchability. Combined experimental and theoretical investigations based on in situ-PXRD, UV/Vis spectroscopy and density functional theory calculations demonstrate deliberate kinetic engineering of photoswitchability based on variations in metal-linker bond strengths. The novel porous frameworks are an important step towards the knowledge-based development of photon driven motors, actuators and release systems.