CO₂ reacts with simple amines in the presence of water to generate dynamic combinatorial libraries of majority (i.e., ammonium carbamates) and minority (i.e., ammonium carbonates) nonisoenergetic covalent adducts. Over the past two decades, our laboratory has reported on a new class of cavitands, namely, dyn[n]arenes, from which a polyanionic macrocycle is a highly efficient receptor for linear polyammoniums that forms [2]pseudorotaxanes in water at neutral pH. Herein, we demonstrate that the formation of [2]pseudorotaxanes shifts the equilibrium of CO₂ capture by polyamines in water toward the quasi-exclusive formation of carbonate adducts, providing the first example of a switch between two competitive and reversible covalent processes triggered by host–guest interactions. In addition, this supramolecular approach to CO₂ capture exhibits enhanced capture efficiency by increasing the state of protonation of complexed vs uncomplexed polyamines. Altogether, we report here that a templating approach can divert the outcome of two reversible covalent chemistries involving nucleophilic additions and acid–base reactions, challenging therefore the common knowledge that noncovalent and covalent bonds operate in separate energy frames.

中文翻译：

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使用主客体化学在非等能动态共价反应之间切换

CO ₂在水存在下与简单胺反应生成大部分（即氨基甲酸铵）和少数（即碳酸铵）非等能共价加合物的动态组合库。在过去的二十年中，我们的实验室报道了一类新的空配体，即达林[n]芳烃，其中的聚阴离子大环化合物是线性聚铵的高效受体，可在中性pH下在水中形成[2]拟轮烷。在此，我们证明[2]拟轮烷的形成将水中多胺捕获CO ₂的平衡转向碳酸盐加合物的准排他形成，提供了由主体触发的两个竞争性和可逆共价过程之间转换的第一个例子– 宾客互动。此外，这种CO ₂捕获的超分子方法通过增加络合多胺与未络合多胺的质子化状态而表现出增强的捕获效率。总而言之，我们在此报告，模板方法可以改变涉及亲核加成和酸碱反应的两种可逆共价化学的结果，因此挑战了非共价键和共价键在不同能量框架中运作的常识。