Molecular Architecture @ MOFs: Designing a Multifunctional Catalyst for the Cascade Reaction of Olefins via Epoxides to Cyclic Carbonates

Abstract

Employing enzymatic reaction cascade principles to synthesize artificial materials with multiple autonomously operating active sites is one of the holy grails in modern catalysis research. In this regard, metal‐organic frameworks (MOFs) are promising host platforms. Yet, applying MOFs as enzyme‐mimicking catalysts is synthetically challenging. Herein, we present a design strategy for the synthesis of porphyrin‐based MOFs for the cascade catalysis of the conversion of olefins to epoxides and their cycloaddition with CO2 to cyclic carbonates. The MOFs feature tunable dual active sites with synthetically controllable metal variations. A clear dependence of the metal combination on the catalytic performance of the MOF catalysts is shown. This work advances the understanding essential for designing sophisticated, multifunctional porphyrin MOFs for efficient one‐pot cascade catalysis.