Visible-Light-Driven Rotation of Molecular Motors in Discrete Supra­molecular Metalla­cycles

The organization of molecular motors in supra­molecular assemblies to allow the amplification and transmission of motion and collective action is an important step toward future responsive systems. Metal-coordination-driven directional self-assembly into supra­molecular metalla­cycles provides a powerful strategy to position several motor units in larger structures with well-defined geometries. Herein, we present a pyridyl-modified molecular motor ligand (MPY) which upon coordination with geometrically distinct di-Pt­(II) acceptors assembles into discrete metalla­cycles of different sizes and shapes. This coordination leads to a red-shift of the absorption bands of molecular motors, making these motorized metalla­cycles responsive to visible light. Photochemical and thermal isomerization experiments demonstrated that the light-driven rotation of the motors in the metalla­cycles is similar to that in free MPY in solution. CD studies show that the helicity inversions associated with each isomerization step in the rotary cycle are preserved. To explore collective motion, the trimeric motor-containing metalla­cycle was aggregated with heparin through multiple electrostatic interactions, to construct a multi-component hierarchical system. SEM, TEM, and DLS measurements revealed that the photo- and thermal-responsive molecular motor units enabled selective manipulation of the secondary supra­molecular aggregation process without dissociating the primary metalla­cycle structures. These visible-light-responsive metalla­cycles, with intrinsic multiple rotary motors, offer prospects for cooperative operations, dynamic hierarchical self-assembled systems, and adaptive materials.