Multicomponent metallo‐supramolecular assembly allows the rational combination of different building blocks. Discrete multifunctional hosts with an accessible cavity can be prepared in a non‐statistical fashion. We employ our shape‐complementary assembly (SCA) method to achieve for the first time integrative self‐sorting of heteroleptic Pd^II cages showing guest‐tunable circularly polarized luminescence (CPL). An enantiopure helicene‐based ligand (M or P configuration) is coupled with a non‐chiral emissive fluorenone‐based ligand (A or B) to form a series of Pd₂L₂L′₂ assemblies. The modular strategy allows to impart the chiral information of the helicenes to the overall supramolecular system, resulting in CPL from the non‐chiral component. Guest binding results in a 4‐fold increase of CPL intensity. The principle offers potential to generate libraries of multifunctional materials with applications in molecular recognition, enantioselective photo‐redox catalysis and information processing.

A strategy to implement four members of the classic coal‐tar dye family, Michler's ketone, methylene blue, rhodamine B, and crystal violet, into [Pd₂L₄] self‐assemblies is introduced. Chromophores were incorporated into bis‐monodentate ligands using piperazine linkers that allow to retain the auxochromic dialkyl amine functionalities required for intense colors deep in the visible spectrum. Upon palladium coordination, ligands with pyridine donors form lantern‐shaped dinuclear cages while quinoline donors lead to strongly twisted [Pd₂L₄] helicates in solution. In one case, single crystal X‐ray diffraction revealed rearrangement to a [Pd₃L₆] ring structure in the solid state. For nine examined derivatives, showing colors from yellow to deep violet, CD spectroscopy discloses different degrees of chiral induction by an enantiomerically pure guest. Ion mobility mass spectrometry allows to distinguish two binding modes. Self‐assemblies based on this new ligand class promise application in chiroptical recognition, photo‐redox catalysis and optical materials.