Visible-Light-Responsive Self-Assembled Complexes: Improved Photoswitching Properties by Metal Ion Coordination

A photoswitchable ligand based on azobenzene is self-assembled with palladium(II) ions to form a [Pd-2(E-L)(4)](4+) cage. Irradiation with 470 nm light results in the near-quantitative switching to a monomeric species [Pd(Z-L)(2)](2+), which can be reversed by irradiation with 405 nm light, or heat. The photoswitching selectivity towards the metastable isomer is significantly improved upon self-assembly, and the thermal half-life is extended from 40 days to 850 days, a promising approach for tuning photoswitching properties.