Nature uses weakly basic residues in conjunction with weakly acidic residues to catalyze challenging heterolytic bond transformations. Here, we show that these cooperative effects can be replicated in a metal–organic framework (MOF) containing bifunctional Brønsted acid–base sites. Using a templating strategy, we show that the colocalization of acid and base sites is key to catalytic activity. Specifically, a thermolabile cross-linker containing tertiary ester and tertiary carbamate linkages is used to tether carboxylic acid and benzylamine pairs in close proximity during framework synthesis. These templated materials are over 4-fold more active aldol condensation catalysts than nontemplated materials containing randomly distributed acid and base sites. Together, this work establishes MOFs as an exciting platform for cooperative acid–base catalysis that couples the advantages of heterogeneous catalysts with the structural precision of enzymes.

中文翻译：

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具有模板化酸碱位点的晶体框架中的协同催化


大自然使用弱碱性残基与弱酸性残基结合来催化具有挑战性的异解键转化。在这里，我们证明这些协同效应可以在含有双功能布朗斯台德酸碱位点的金属有机框架（MOF）中复制。使用模板策略，我们表明酸和碱位点的共定位是催化活性的关键。具体来说，含有叔酯和叔氨基甲酸酯键的热不稳定交联剂用于在框架合成过程中将羧酸和苄胺对紧密相连。这些模板化材料的羟醛缩合催化剂活性比含有随机分布的酸碱位点的非模板化材料高4倍以上。总之，这项工作将 MOF 建立为一个令人兴奋的酸碱协同催化平台，将多相催化剂的优点与酶的结构精度结合起来。