Encapsulated Dye in Coordination-Assembled Octahedron for Visible-Light-Driven Proton Reduction and Nitroaromatic Hydrogenation

To mimic the finely tuned natural photosynthetic systems, a large metal–organic octahedron was synthesized by one-pot self-assembly with modified triphenylamine ligands and redox-active cobalt ions. By encapsulating an organic dye, fluorescein (Fl), within the inner cavity of the octahedron, the host–guest supramolecular system was provided for light-driven hydrogen production. The intimate distance between the redox site and the photosensitizer in the supramolecular metal–organic cage allowed the photoinduced electrons to transfer from the excited state Fl* to the redox cobalt center in a pseudo-intramolecular pathway. The supramolecular system showed good performance in light-driven hydrogen production and the reduction of nitroaromatic compounds. Control experiments based on a mononuclear compound resembling a cobalt corner of the octahedron and inhibitor competition provided evidence of enzyme-like catalytic behavior. The supramolecular reaction pathways within confined spaces contribute to the superior activity of the host–guest system.