Stereoselective C−C Oxidative Coupling Reactions Photocatalyzed by Zwitterionic Ligand Capped CsPbBr₃ Perovskite Quantum Dots

Abstract

Semiconductor quantum dots (QDs) have attracted tremendous attention in the field of photocatalysis, owing to their superior optoelectronic properties for photocatalytic reactions, including high absorption coefficients and long photogenerated carrier lifetimes. Herein, by choosing 2‐(3,4‐dimethoxyphenyl)‐3‐oxobutanenitrile as a model substrate, we demonstrate that the stereoselective (>99 %) C−C oxidative coupling reaction can be realized with a high product yield (99 %) using zwitterionic ligand capped CsPbBr3 perovskite QDs under visible light illumination. The reaction can be generalized to different starting materials with various substituents on the phenyl ring and varied functional moieties, producing stereoselective dl‐isomers. A radical mediated reaction pathway has been proposed. Our study provides a new way of stereoselective C−C oxidative coupling via a photocatalytic means using specially designed perovskite QDs.

A covalent organic framework as a photocatalyst for window ledge cross-dehydrogenative coupling reactions

“…As one of the key strategies of solar energy conversion, photocatalysis, which can directly transform solar energy into chemical energy, has made tremendous progress in the past few decades. 2,3 Hereinto, by inspiring the synergy of the precious advantages of photosynthesis with the utilization of free and renewable solar energy, ''window ledge'' chemistry, that is, photocatalytic reactions directly activated by natural sunlight, has attracted much attention, and exhibited great potential in organic photosynthesis, such as alkylation, 4 cycloaddition and synthesis of aromatic ketones. 5 Regarding its practical applications, it is still challenging to formulate the structure-property relationships and to optimize the photophysical properties of photocatalysts, in order to further improve their catalytic activity and recyclability.…”

Ion exchange for halide perovskite: From nanocrystal to bulk materials

“…Depending on the ultrahigh photoluminescence quantum yield (PLQY), narrow emission FWHM and highly emissive tunability, the 0D perovskite nanomaterials with quantum confinement size have attracted much attentions and made great strides in the past several years, [19,[67][68][69][70][71][72][73][74] such as the successful display applications recently reported by Zhong et al [75][76] Except for the size control achieved within the synthesis procedure (thermal injection, [68] ligand-assisted reprecipitation, [19] and so on), ion exchange provides an additional path to modify the physicochemical properties of 0D halide perovskites. We will discuss the ion exchange for 0D halide perovskites according to the different crystallographic components in this section.…”

Lead‐Free Cs2AgSbCl6 Double Perovskite Nanocrystals for Effective Visible‐Light Photocatalytic C−C Coupling Reactions

“…Lead halide perovskite nanocrystals (NCs) have been utilized in versatile realms including solar cells, [1,2] lasers, [3] photodetectors, [4,5] and light‐emitting diodes, [6,7] benefiting from their remarkable optoelectronic and photophysical properties. Meanwhile, lead halide perovskite NCs have also shown great promise as efficient photocatalysts for organic reactions such as degradations, [8–19] polymerizations, [20–24] oxidations, [25–32] isomerizations, [33] aminomethylations, [34] aromatizations, [35] heterocyclizations, [36,37] and C−C, [36,38–42] C−O, [36] C−S, [43] S−S, or C−P bond‐forming reactions, [44] taking advantage of their high extinction coefficients, [45] excellent charge transport properties, [46] low exciton binding energy, [47,48] as well as tunable band gaps [49,50] . Additionally, compared with transition metal complexes or organic dyes, perovskite NCs as photocatalysts exhibit several appealing superiorities.…”