Photo‐regulated synergistic catalysis of acid and basic sites in metal–organic framework

Abstract

AbstractEnzymes have flexible structures and can modulate the multiple catalytic sites efficiently for synergistic catalysis. Inspired by enzymes, various artificial catalysts have been designed, while controllable synergistic effects in artificial catalysts have never been reported. Here, we report the first example of photo‐regulated synergistic catalyst (PRSC) and the synergistic effects between acidic and basic sites can be regulated by light. PRSCs have acidic sites on pore walls and basic sites on pendant azobenzene groups, and photo‐regulation is achieved through azobenzene isomerization. In the cascade reaction of converting benzaldehyde dimethyl acetal (BA) to benzylidenemalononitrile (BM), the PRSC shows a change of up to 33.6% in BM yield. Mechanism exploration indicates that cis azobenzene makes the catalytic system more stable. The promoted adsorption energy of the reactant malononitrile (MN) on basic sites and the activated C atom of MN that connects to methylene groups are responsible for the tunable synergistic effects of PRSCs.