Photoswitchable Metal–Organic Framework as a Smart Nanoreactor for Ultraviolet Light-Enhanced Confined Catalysis

Confined catalysis, where a chemical reaction is accommodated within a nanoscale host, provides an effective approach to control the pathways and outcomes of catalytic transformations. However, the confinement effect is typically limited to a fixed rate and/or selectivity once the nanohost is chosen. Herein, we developed a photoresponsive metal-organic framework (MOF) as a "smart" nanohost to realize ultraviolet (UV) light-enhanced confined catalysis of Knoevenagel condensation. Photoresponsive MOF of <b>Zn-ADA</b> was thus prepared by solvothermal strategy where azobenzene-4,4'-dicarboxylic acid (ADA) was used as the photoactive linker to coordinate with zinc nitrate. Characterization results suggested that UV light could decrease the pore size of <b>Zn-ADA</b> due to suppressed bending of the azobenzene-containing ADA linker in <b>Zn-ADA</b>. It enforced the proximity between substrates and catalytic groups within the confined space, and thus enhanced the confinement effect on Knoevenagel condensation. The UV light-enhanced confined catalysis enabled the translation of light stimulus into chemical signal, which may open up new control on the basis of the specific reaction field.