Azulene, a blue structural isomer of naphthalene, is introduced as the backbone for a new family of Pd(II)-based self-assemblies. Three organic ligands, equipped with varying donor groups, produce three [PdL] cages of different cavity dimensions. Unexpectedly, the addition of organic disulfonate guests to the smallest lantern-shaped cage (featuring pyridine donors) led to a rapid and quantitative transformation to a distorted-tetrahedral [PdL] species. On the contrary, [PdL] cages formed from ligands with isoquinoline donors either just encapsulated the guests or showed no interaction. The tetrahedral species could be fully reverted back to its original [PdL] topology by capturing the guest by another, stronger binding [PdL'] coordination cage, narcissistically self-sorting from the first cage. The azulenes, serving as colored hydrocarbon backbones of minimal atom count, allow one to follow cage assembly and guest-induced transformation by the naked eye. Furthermore, we propose that their peculiar electronic structure influences the system's assembly behavior.
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