Narcissistic self-sorting vs. statistic ligand shuffling within a series of phenothiazine-based coordination cages.

Previously, we introduced a series of anion-binding interpenetrated double-cages based on phenothiazine and its mono- and di-S-oxygenated derivatives. Here, we complete the structural comparison of the three related assemblies by an X-ray single crystal analysis of the sulfone derivative. We further show that the three palladium cages coexist in solution upon post-assembly mixing due to the very slow ligand exchange whereas treatment of binary mixtures of the corresponding ligands with Pd(II) leads to the formation of mixed cages comprising a statistical ligand distribution. In contrast, mixtures of one of these ligands with a shorter ligand derivative lead to narcissistic self-assembly into a double-cage and a coexisting small monomeric cage, regardless of the order of mixing and Pd(II) addition.