Nanostructured Molecular Systems and Materials Group, Departamento de Química Orgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, 28049 Madrid, Spain.
Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain.
J Am Chem Soc. 2022 Mar 30;144(12):5450-5460. doi: 10.1021/jacs.1c13295. Epub 2022 Mar 19.
Self-sorting phenomena are the basis of manifold relevant (bio)chemical processes where a set of molecules is able to interact with no interference from other sets and are ruled by a number of codes that are programmed in molecular structures. In this work, we study, the relevance of chelate cooperativity as a code for achieving high self-sorting fidelities. In particular, we establish qualitative and quantitative relationships between the cooperativity of a cyclic system and the self-sorting fidelity when combined with other molecules that share identical geometry and/or binding interactions. We demonstrate that only systems displaying sufficiently strong chelate cooperativity can achieve quantitative narcissistic self-sorting fidelities either by dictating the distribution of cyclic species in complex mixtures or by ruling the competition between the intra- and intermolecular versions of a noncovalent interaction.
自分拣现象是多种相关（生物）化学过程的基础，在这些过程中，一组分子能够在不受其他组干扰的情况下相互作用，并受一些编码规则的约束，这些编码规则被编程到分子结构中。在这项工作中，我们研究了螯合协同作用作为实现高自分拣保真度的代码的相关性。特别是，我们建立了一个循环系统的协同作用与与其他具有相同几何形状和/或结合相互作用的分子结合时的自分拣保真度之间的定性和定量关系。我们证明，只有显示出足够强的螯合协同作用的系统才能通过控制复杂混合物中环型物质的分布或以非共价相互作用的分子内和分子间版本之间的竞争来实现定量的自恋自分拣保真度。
