Visible light-mediated C (sp3)-H bond functionalization inside an all-organic nanocavity.
Chem Commun (Camb)
; 59(88): 13143-13146, 2023 Nov 02.
Article
em En
| MEDLINE
| ID: mdl-37849327
ABSTRACT
Ultrafast C-H bond activation and functionalization in confinement using visible light will enable engineering chemical reactions with extraordinary speed and selectivity. To provide a transition metal-free route, here we demonstrate C-H bond activation reactions on poly-aromatic hydrocarbons (PAH) in all-organic cationic nanocage ExBox4+ for the first time. Visible light excitation in the host-guest charge transfer (CT) state allows the formation of oxidized photoproducts with high selectivity. Mechanistic understanding of this CT-mediated photoreaction using femtosecond broadband transient absorption revealed a few â¼100 ps timescale for C-H bond breaking on the attached -CH3 group via sequential electron transfer and proton transfer steps. We envision that our photosensitizer-free method will open up new avenues to pursue organic reactions using cavities that could serve both as photoredox catalysts and hosts for reactive reaction intermediates.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Chem Commun (Camb)
Assunto da revista:
QUIMICA
Ano de publicação:
2023
Tipo de documento:
Article
País de afiliação:
Índia