A photosensitizing decatungstate-based MOF as heterogeneous photocatalyst for the selective C–H alkylation of aliphatic nitriles

Abstract

The efficient photosensitizing of decatungstate-based MOF with 1D channels was achieved via in situ synthesis under solvothermal conditions for light driven acceleration of β- or γ-site C-H alkylation of aliphatic nitriles. The high catalytic efficiency, excellent size selectivity, high stability and good recyclability of the photocatalyst offer an environmentally-friendly route for widening the scope of accessible nitriles in both laboratory and industry.

Applications of inorganic‐organic hybrid architectures based on polyoxometalates in catalyzed and photocatalyzed chemical transformations

“…In another study, a solvothermal synthetic method is used to obtain a decatungstate‐based MOF with 1D channels. The MOF of [Cu 4 (4,4′‐bpy) 6 Cl 2 (W 10 O 32 )]•3H 2 O exhibited remarkable photocatalytic activities for the β‐ or γ‐site C–H alkylation of aliphatic nitriles under mild reaction conditions . The photoactive [W 10 O 32 ] 4– POMs are embedded in the pores of Cu–BPY via electrostatic attraction.…”

“…Schematic representation of the photocatalytic reaction and the crystal‐type I to crystal‐type II transformation induced by catalytic substrate encapsulation. Figure reproduced from Ref., with permission of the copyright holders…”

“…The MOF of [Cu 4 (4,4′-bpy) 6 Cl 2 (W 10 O 32 )]•3H 2 O exhibited remarkable photocatalytic activities for the βor γ-site C-H alkylation of aliphatic nitriles under mild reaction conditions. [124] The photoactive [W 10 O 32 ] 4-POMs are embedded in the pores of Cu-BPY via FIGURE 10 A new approach to merge Cu-catalysis/Ru-photocatalysis within one single MOF for oxidative C-C bond formation. Figure reproduced from Ref., [123] with permission of the copyright holders.…”

“…[128] In this plausible reaction mechanism for the photoreduction of CO 2 by a rhenium(I)-POM hybrid compound, it is believed that POM anion acts as photo-sensitizer, electron reservoir and electron donor. [124] with permission of the copyright holders 4 | CONCLUSIONS AND PROSPECTS Design and preparation of the active, selective, recyclable and environmentally benign catalysts has become an attractive issue in recent scientific research in the area of catalysis as well as photocatalysis. In this regard, POMs are frequently considered as unrivaled and outstanding candidates due to their unique and fascinating possessions, such as tunable redox and acid-base properties, inherent resistance to oxidative decomposition, high thermal stability, and impressive sensitivity to light because of their multiple active sites, including protons, metal ions, and oxygen atoms.…”

Selective C(sp3)−H Aerobic Oxidation Enabled by Decatungstate Photocatalysis in Flow

“…[12, 13b] Among the different reported photocatalysts,d ecatungstate (DT) has proved to be aversatile and inexpensive HAT catalyst which can readily perform hydrogen abstraction on C(sp 3 ) À Hfragments upon activation by irradiation with nearultraviolet light. [14] This strategy allowed for the construction of numerous CÀC, [15] CÀSi, [16] CÀN, [17] and CÀF [18] bonds. [15a,19] Intrigued by these seminal reports,w ew ondered if DT catalysis could be used to effect selective C(sp 3 )ÀHa erobic oxidation.…”