Dynamic Covalent Self-Sorting and Kinetic Switching Processes in Two Cyclic Orders: Macrocycles and Macrobicyclic Cages

Dynamic covalent component self-sorting processes have been investigated for constituents of different cyclic orders, macrocycles and macrobicyclic cages based on multiple reversible imine formation. The progressive assembly of the final structures from dialdehyde and polyamine components involved the generation of kinetic products and mixtures of intermediates which underwent component selection and self-correction to generate the final thermodynamic constituents. Importantly, constitutional dynamic networks (CDNs) of macrocycles and macrobicyclic cages were set up either from separately prepared constituents or by in situ assembly from their components. Over time, these CDNs underwent conversion from a kinetically trapped out-of-equilibrium distribution of constituents to the thermodynamically self-sorted one through component exchange in different dimensional orders.