Investigating the self-assembly and self-sorting behaviour of dynamic covalent organic architectures makes possible the parallel generation of multiple discrete products in a single one pot procedure. We here report the self-assembly of covalent organic macrocycles and macrobicyclic cages from dialdehyde and polyamine components via multiple [2 + 2] and [3 + 2] polyimine condensations. Furthermore, component self-sorting processes have been monitored within the dynamic covalent libraries formed by these macrocycles and macrobicyclic cages. The progressive assembly of the final structures involves intermediates which undergo component selection and self-correction to generate the final thermodynamic constituents. The homo-self-sorting observed seems to involve entropic factors, as the homoleptic species present a higher symmetry than the competing heteroleptic ones. This study not only emphasizes the importance of an adequate design of the components of complex self-sorting systems, but also verifies the conjecture that systems of higher complexity may generate simpler outputs through the operation of competitive self-sorting.
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