A Visible-Light-Responsive Octahedral Cage for Efficient and Selective Cross-[2 + 2] Cycloadditions

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Abstract
Host-guest complexation enhances or even alters photoreaction selectivity by preorganizing substrates within the host's confined cavities. Since most previous hosts exhibited no visible-light absorption, at least one of the reactants needed to be an aromatic compound with UV-light absorption. Here, we developed a visible-light-responsive M6L4 octahedral cage that retains the encapsulation ability of standard M6L4 cages by simply replacing the photoinert metal unit at every vertex with a photoactive cyclometalated Pt(II) unit. This design enabled efficient visible-light-induced cross-[2 + 2] cycloadditions of inert substrates, demonstrating perfect stereo- and site-selectivity via confinement. The selective cross-[2 + 2] cycloaddition was achieved even catalytically, which was impossible with previous M6L4 cages.
Funding Information
  • Japan Agency for Medical Research and Development (JP24zf0227103)
  • Japan Society for the Promotion of Science (JP23H01783, JP24H00054)

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