Liquid‐Phase Epitaxially Grown Metal–Organic Framework Thin Films for Efficient Tandem Catalysis Through Site‐Isolation of Catalytic Centers

Abstract A functional metal–organic framework (MOF) composed of robust porphyrinic material (RPM) based on the pillared‐paddlewheel topology is prepared with large 3 D channels, and is used to perform a tandem epoxidation/CO 2 insertion reaction. The designated system benefits from two metalloporphyrins: 1) a Mn‐porphyrin, which catalyzes the epoxidation of an olefin substrate, and 2) a Zn‐porphyrin, which catalyzes the epoxide opening. By using an automated liquid‐phase epitaxial growth system, the RPM‐MOF is also prepared in layer‐by‐layer fashion as an ultrathin film on a self‐assembled‐monolayer‐coated silicon platform. Deployed as a tandem catalyst, the film version yields a substantially higher catalytic turnover number for tandem methoxy‐styrene epoxidation followed by CO 2 insertion than the bulk crystalline MOF samples.