Modulation of a Supramolecular Figure‐of‐Eight Strip Based on a Photoswitchable Stiff‐Stilbene

The preparation, assembly and dynamic properties of photoswitchable bisphosphine ligands based on the stiff‐stilbene scaffold are reported. Directional bonding and coordination‐induced assembly allow complexation of these ligands with palladium(II), resulting in the formation of discrete metallo‐supramolecular entities. While the Z isomer forms a simple bidentate metallo‐macrocycle, an intricate double helicate figure‐of‐eight dimer is observed with the E ligand. Topologically 3D complexes can thus be obtained from 2D ligands. Upon irradiation with UV light, isomerization of the ligands allows control of the architecture of the formed complexes, resulting in a light‐triggered modulation of the supramolecular topology. Furthermore, a mechanistic investigation unveiled the dynamic nature of the helicate chirality, where a transmission of motion from the palladium centers yields an „eight‐to‐eight“ inversion.