Heteroleptic coordination cages, nonstatistically assembled from a set of matching ligands, can be obtained by mixing individual components or via cage-to-cage transformations from homoleptic precursors. Based on the latter approach, we here describe a new level of self-sorting in coordination cage systems, namely, 'heteromeric completive self-sorting'. Here, two heteroleptic assemblies of type Pd₂A₂B₂ and Pd₂A₂C₂, sharing one common ligand component A but differing in the other, are shown to coexist in solution. This level of self-sorting can be reached either from a statistical mixture of assemblies based on some ligands B and C or, alternatively, following a first step of integrative self-sorting giving a distinct Pd₂B₂C₂ intermediate. While subtle enthalpic factors dictate the outcome of the self-sorting, we found that it is controllable. From a unique set of three ligands, we demonstrate the transition from strict integrative self-sorting forming a Pd₂AB₂C cage to heteromeric completive self-sorting to give Pd₂A₂B₂ and Pd₂A₂C₂ by variation of the ligand ratio. Cage-to-cage transformations were followed by NMR and MS experiments. Single crystal X-ray structures for three new heteroleptic cages were obtained, impressively highlighting the versatility of ligand A to either form a π-stacked trans-figure-of-eight arrangement in Pd₂A₂B₂ or occupy two cis-edges in Pd₂A₂C₂ or only a single edge in Pd₂AB₂C. This study paves the way toward the control of heteroleptic cage populations in a systems chemistry context with emerging features such as chemical information processing, adaptive guest selectivity, or stimuli-responsive catalytic action.

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