Visible-light photocatalysis and electrocatalysis are two powerful strategies for the promotion of chemical reactions that have received tremendous attention in recent years. In contrast, processes that combine these two modalities, an area termed electrophotocatalysis, have until recently remained quite rare. However, over the past several years a number of reports in this area have shown the potential of combining the power of light and electrical energy to realize new catalytic transformations. Electrophotocatalysis offers the ability to perform photoredox reactions without the need for large quantities of stoichiometric or superstoichiometric chemical oxidants or reductants by making use of an electrochemical potential as the electron source or sink. In addition, electrophotocatalysis is readily amenable to the generation of open-shell photocatalysts, which tend to have exceptionally strong redox potentials. In this way, potent yet selective redox reactions have been realized under relatively mild conditions. This Perspective highlights recent advances in the area of electrophotocatalysis and provides some possible avenues for future work in this growing area.
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http://dx.doi.org/10.1021/jacs.2c01914 | DOI Listing |
Res Sq
November 2024
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853, United States.
The reductive functionalization of inert substrates like chloroarenes is a critical yet challenging transformation relevant to both environmental remediation and organic synthesis. Combining electricity and light is an emerging approach to access the deeply reducing potentials required for single electron transfer to chloroarenes, yet this approach is held back by the poor stability and mechanistic ambiguity of current homogeneous systems. Incorporating redox-active moieties into insoluble organic materials represents a promising strategy to unlock new heterogeneous catalytic activity while improving catalyst stability.
View Article and Find Full Text PDFChem Rev
November 2024
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States.
Electrocatalysis and photocatalysis have been the focus of extensive research efforts in organic synthesis in recent decades, and these powerful strategies have provided a wealth of new methods to construct complex molecules. Despite these intense efforts, only recently has there been a significant focus on the combined use of these two modalities. Nevertheless, the past five years have witnessed rapidly growing interest in the area of electrophotocatalysis.
View Article and Find Full Text PDFPhys Chem Chem Phys
August 2024
MagnetoCat SL, Calle General Polavieja 9, 3 Izq 03012 Alicante, Spain.
Catalysis is a quantum phenomenon enthalpically driven by electronic correlations with many-particle effects in all of its branches, including electro-photo-catalysis and electron transfer. This means that only probability amplitudes provide a complete relationship between the state of catalysis and observations. Thus, in any atomic system material), competing space-time electronic interactions coexist to define its (related) properties such as stability, (super)conductivity, magnetism (spin-orbital ordering), chemisorption and catalysis.
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October 2024
Ordered Matter Science Research Center College of Chemistry and Chemical Engineering, Southeast University, 211189, Nanjing, P. R. China.
The lone pair electrons in the electronic structure of molecules have been a prominent research focus in chemistry for more than a century. Stable s lone pair electrons significantly influence material properties, including thermoelectric properties, nonlinear optical properties, ferroelectricity, and electro(photo)catalysis. While major advances have been achieved in understanding the influence of lone pair electrons on material characteristics, research on this effect in organic-inorganic hybrid materials is in its initial stage.
View Article and Find Full Text PDFBeilstein J Org Chem
July 2024
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
We report a practical and sustainable electrophotochemical metal-catalyzed protocol for decarboxylative cyanation of simple aliphatic carboxylic acids. This environmentally friendly method features easy availability of substrates, broad functional group compatibility, and directly converts a diverse range of aliphatic carboxylic acids including primary and tertiary alkyl acids into synthetically versatile alkylnitriles without using chemical oxidants or costly cyanating reagents under mild reaction conditions.
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