Solvent‐Controlled Separation of Integratively Self‐Sorted Pd ₂ L ^A ₂ L ^B ₂ Coordination Cages

Abstract The integrative implementation of multiple different components into metallosupramolecular self‐assemblies requires sophisticated strategies to avoid the formation of statistical mixtures. Previously, the key focus was set on thermodynamically driven reactions of simple homoleptic into complex heteroleptic structures. Using Pd 2 L A 2 L B 2 ‐type coordination cages, we herein show that integrative self‐sorting can be reversed by a change of solvent (from DMSO to MeCN) to favor narcissistic re‐segregation into coexisting homoleptic species Pd 2 L A 4 and Pd 3 L B 6 . Full separation (“unsorting”) back to a mixture of the homoleptic precursors was finally achieved by selective precipitation of Pd 3 L B 6 with anionic guest G 1 from MeCN, keeping pure Pd 2 L A 4 in solution. When a mixture of homoleptic Pd 3 L B 6 and heteroleptic Pd 2 L A 2 L B 2 is exposed to a combination of two different di‐anions ( G 1 and G 2 ) in DMSO, selective guest uptake gives rise to two defined coexisting host–guest complexes. A joint experimental and deep theoretical investigation via liquid‐state integral equation theory of the reaction thermodynamics on a molecular level accompanied by solvent distribution analysis hints at solvent expulsion from Pd 2 L A 4 to favor the formation of Pd 2 L A 2 L B 2 in DMSO as the key entropic factor for determining the solvent‐specific modulation of the cage conversion equilibrium.