Efficient amine oxidation using metal–organic framework photocatalysts for aminoalkyl radical-mediated halogen-atom transfer

Abstract

The utilize of amines, serving typically as electron-donating sacrificial agents, to boost catalytic performance using MOFs is very common in various photocatalytic reactions. However, the reactivity of the oxidized amine...

Integrating Hybrid Perovskite Nanocrystals into Metal–Organic Framework as Efficient S-Scheme Heterojunction Photocatalyst for Synergistically Boosting Controlled Radical Photopolymerization under 980 nm NIR Light

“…59 It has been reported that the hydroxyl groups of TEOA can be oxidized by MOFs to aldehyde groups and further generate aldehyde-bearing α-aminoalkyl radicals. 60 The adducts of MMA and TEOA catalyzed by MAPbI 3 @ PCN-222(10%) were detected by 1 H NMR spectroscopy (unpurified, Figure S8), 61 which distinctly authenticated the generation of reactive aldehyde-bearing α-aminoalkyl radicals from TEOA in the photopolymerization. Indeed, its formation was confirmed by mass spectrometry analysis of the reaction mixture (Figure S9).…”

“…Indeed, its formation was confirmed by mass spectrometry analysis of the reaction mixture (Figure S9). The oxidation potential of TEOA is 0.59 V (vs SCE, 0.83 V vs NHE), while the VB of MAPbI 3 is 0.65 V (vs NHE). The calculation shows that MAPbI 3 cannot oxidize TEOA, while PCN-222 with 1.34 V (vs NHE) VB can oxidize TEOA.…”

“…(vs SCE, 0.83 V vs NHE),61 while the VB of MAPbI 3 is 0.65 V (vs NHE). The calculation shows that MAPbI 3 cannot oxidize TEOA, while PCN-222 with 1.34 V (vs NHE) VB can oxidize TEOA.…”

Light‐promoted Selective Reduction of Nitroarenes to Azoxy‐, Azo‐ and Hydrazo‐compounds Catalyzed by Bismuth Porphyrin Metal Organic Framework

“…[40][41][42][43][44][45][46] As a subclass of the MOFs family, porphyrin MOFs have been widely applied in the field of photocatalysis because of their highly conjugated heterocyclic structures, broad absorption in the visible light region, and flexible structural compositions. [47][48][49] For instance, Huang et al [50] reported that a photocatalytic catalyst was developed for the CO 2 cyclization reaction by introducing Bi atoms into the porphyrin units of PCN-224 (typical porphyrin MOF). It was found that the introduction of light and the unique synergy between Bi and Zr atoms in the MOFs activate inert CO 2 and lower the barrier for the cycloaddition.…”

“…Meanwhile, heterogeneous catalyst metal organic frameworks (MOFs) have shown excellent catalytic performances in a variety of challenging photodynamic reactions, owing to their diverse structural compositions, abundant active sites, specific surface area [40–46] . As a subclass of the MOFs family, porphyrin MOFs have been widely applied in the field of photocatalysis because of their highly conjugated heterocyclic structures, broad absorption in the visible light region, and flexible structural compositions [47–49] . For instance, Huang et al [50] reported that a photocatalytic catalyst was developed for the CO 2 cyclization reaction by introducing Bi atoms into the porphyrin units of PCN‐224 (typical porphyrin MOF).…”