Ultrafast photoactivation of C─H bonds inside water-soluble nanocages.

Light energy absorbed by molecules can be harnessed to activate chemical bonds with extraordinary speed. However, excitation energy redistribution within various molecular degrees of freedom prohibits bond-selective chemistry. Inspired by enzymes, we devised a new photocatalytic scheme that preorganizes and polarizes target chemical bonds inside water-soluble cationic nanocavities to engineer selective functionalization. Specifically, we present a route to photoactivate weakly polarized sp3 C─H bonds in water via host-guest charge transfer and control its reactivity with aerial O2. Electron-rich aromatic hydrocarbons self-organize inside redox complementary supramolecular cavities to form photoactivatable host-guest charge transfer complexes in water. An ultrafast C─H bond cleavage within ~10 to 400 ps is triggered by visible-light excitation, through a cage-assisted and solvent water-assisted proton-coupled electron transfer reaction. The confinement prolongs the lifetime of the carbon-centered radical to enable a facile yet selective reaction with molecular O2 leading to photocatalytic turnover of oxidized products in water.