A new triazine-based organized 2D covalent organic framework (COF), namely, TRITER-2, has been built through combinatorial copolymerization between 4,4'-biphenyldicarbaldehyde and a triamine 1,3,5-tris-(4-aminophenyl) triazine (TAPT). This highly crystalline organic polymeric...
Photocatalytic carboxylation of Aryl derivatives was demonstrated under the atmospheric pressure of CO2 using the mesoporous Covalent Organic Framework (COF) as the active photocatalyst with Triethylamine (TEA) as a sacrificial...
Direct photochemical carboxylation of C(sp3)–H
bonds with CO2 is an uphill task and it has attracted increasing
attention. In the present study, we report an elegant strategy for
visible-light-triggered C(sp3)-H carboxylation of amines
with CO2 into α-amino acids using a stable crystalline
polyimide-based covalent organic framework (PI-COF) as an efficient
heterogeneous photocatalyst and NiO nanoparticles (NiO NPs) as a cocatalyst
under ambient conditions (room temperature and atmospheric CO2 pressure). Diverse amino acids are produced in moderate-to-high
yields. This methodology tolerates a range of functional groups and
displays remarkable regioselectivity. Various drugs were effectively
achieved using this light-assisted approach. The high chemical stability
of the COF and its strong interactions with NiO NPs renders the catalytic
system to be highly recyclable (i.e., over five times). More interestingly,
this photoinduced carboxylation reaction occurred without the involvement
of any sacrificial electron donors. Based on computational (DFT) investigations,
a tentative mechanism revealed the formation of CO2 radical
anion at the conduction band (CB) of the COF via single electron transfer
mediated by NiO nanoparticles which combined with amine radical cation
at the valence band of the COF to form α-amino acid.
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