Enzymes 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.

中文翻译：

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金属有机框架中酸碱位点的光调控协同催化

酶具有灵活的结构，可以有效地调节多个催化位点以实现协同催化。受酶的启发，人们设计了各种人工催化剂，但人工催化剂的可控协同效应尚未见报道。在这里，我们报告了光调节协同催化剂（PRSC）的第一个例子，酸性和碱性位点之间的协同效应可以通过光调节。PRSCs 的孔壁上有酸性位点，偶氮苯侧基上有碱性位点，光调节是通过偶氮苯异构化实现的。在苯甲醛二甲基缩醛 (BA) 转化为亚苄基丙二腈 (BM) 的级联反应中，PRSC 的 BM 产率变化高达 33.6%。机制探索表明顺式偶氮苯使催化体系更加稳定。反应物丙二腈（MN）在碱性位点上的吸附能以及与亚甲基连接的MN的活化C原子是PRSCs可调协同效应的原因。