Solvent- and metal-gated coordination diversity in a dynamic aminal ligand.

Within the broad landscape of dynamic covalent chemistry (DCC), the coordination chemistry of primary-amine-based aminals has received comparatively little systematic investigation. Here we demonstrate that a primary-amine-based dynamic covalent aminal (LA2) can serve as an adaptive scaffold for coordination chemistry diversity, where solvent and metal ion choice govern distinct outcomes. Coordination stabilizes otherwise transient ligand forms and directs divergent pathways: Co(III) stabilizes hemiaminalates in methanol, with [Co(LO2)2](ClO4) exhibiting fluxional behavior, and templates macrocyclization in acetonitrile to yield [Co(LM)](ClO4)3; Cu(II) affords hemiaminal and hemiaminal ether complexes, and Fe(III) promotes pyridinium dimerization to give cis-[(LI2)2](ClO4). These findings establish that dynamic ligands can actively generate structural diversity in metal complexes, opening new directions for adaptive ligand design and functional coordination architectures.