A self-assembled macrocycle with a non-closed structure for hierarchically upgraded self-assembly.

Here, a [3 + 10] non-closed macrocycle was serendipitously self-assembled, incorporating two monovalent diamines, each with an unreacted amino group. These are selectively removed via imine exchange, yielding a dialdehyde intermediate. This precursor facilitates hierarchical self-assembly into structures comprising two types of amine building blocks unattainable by one-pot synthesis.