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


ABSTRACT: 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.

SUBMITTER: Das A 

PROVIDER: S-EPMC6386559 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature

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

Das Ankita A   Mandal Imon I   Venkatramani Ravindra R   Dasgupta Jyotishman J  

Science advances 20190222 2


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 sp<sup>3  ...[more]

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