Coal-Tar Dye-based Coordination Cages and Helicates

A strategy to implement four members of the classic coal-tar dye family, Michler's ketone, methylene blue, rhodamine B, and crystal violet, into [Pd₂ L₄ ] 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 [Pd₂ L₄ ] helicates in solution. In one case, single crystal X-ray diffraction revealed rearrangement to a [Pd₃ L₆ ] 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.