Anthrazoline Photocatalyst for Promoting Esterification and Etherification Reactions via Photoredox/Nickel Dual Catalysis

Zhu, Xiaolin; Fan, Qiujin; Luo, Wei; Wang, Danfeng; Jia, Yihui; Li, Heyang; Wang, Zhen; Xiao, Qi; He, Xiaoming

doi:10.1002/cjoc.202200663

“…Furthermore, drawing from insights in colloid science, the incorporation of charged NÀ H + group is expected to enhance colloid stability and regulate the morphology of self-assemblies. Additionally, N-heterocyclic π-conjugated anthrazolines are appreciated as photocatalysts [34,35] due to their broad light absorption, strong electron-deficiency, high electron mobility, and a propensity to form highly ordered nanostructures. [36] Based on these concepts, anthrazoline-based photocatalysts present an excellent platform for investigating the effect of symmetry breaking on exciton dissociation and photocatalytic performance in supramolecular assemblies.…”

Section: Introductionmentioning

confidence: 99%

Enhancing Built‐in Electric Fields via Molecular Symmetry Modulation in Supramolecular Photocatalysts for Highly Efficient Photocatalytic Hydrogen Evolution

Zhu,

Jia,

Liu

et al. 2024

Angewandte Chemie

Self Cite

0

View full text Add to dashboard Cite

Nature‐inspired supramolecular self‐assemblies are attractive photocatalysts, but their quantum yields are limited by poor charge separation and transportation. A promising strategy for efficient charge transfer is to enhance the built‐in electric field by symmetry breaking. Herein, an unsymmetric protonation, N‐heterocyclic π‐conjugated anthrazoline‐based supramolecular photocatalyst SA‐DADK‐H+ was developed. The unsymmetric protonation breaks the initial structural symmetry of DADK, resulting in ca. 50‐fold increase in the molecular dipole, and facilitates efficient charge separation and transfer within SA‐DADK‐H+. The protonation process also creates numerous active sites for H2O adsorption, and serves as crucial proton relays, significantly improving the photocatalytic efficiency. Remarkably, SA‐DADK‐H+ exhibits an outstanding hydrogen evolution rate of 278.2 mmol g‐1 h‐1 and a remarkable apparent quantum efficiency of 25.1% at 450 nm, placing it among the state‐of‐the‐art performances in organic semiconductor photocatalysts. Furthermore, the versatility of the unsymmetric protonation approach has been successfully applied to four other photocatalysts, enhancing their photocatalytic performance by 39 to 533 times. These findings highlight the considerable potential of unsymmetric protonation induced symmetry breaking strategy in tailoring supramolecular photocatalysts for efficient solar‐to‐fuel production.

show abstract

Enhancing Built‐in Electric Fields via Molecular Symmetry Modulation in Supramolecular Photocatalysts for Highly Efficient Photocatalytic Hydrogen Evolution

Zhu,

Jia,

Liu

et al. 2024

Angew Chem Int Ed

Self Cite

2

0

View full text Add to dashboard Cite

Nature‐inspired supramolecular self‐assemblies are attractive photocatalysts, but their quantum yields are limited by poor charge separation and transportation. A promising strategy for efficient charge transfer is to enhance the built‐in electric field by symmetry breaking. Herein, an unsymmetric protonation, N‐heterocyclic π‐conjugated anthrazoline‐based supramolecular photocatalyst SA‐DADK‐H+ was developed. The unsymmetric protonation breaks the initial structural symmetry of DADK, resulting in ca. 50‐fold increase in the molecular dipole, and facilitates efficient charge separation and transfer within SA‐DADK‐H+. The protonation process also creates numerous active sites for H2O adsorption, and serves as crucial proton relays, significantly improving the photocatalytic efficiency. Remarkably, SA‐DADK‐H+ exhibits an outstanding hydrogen evolution rate of 278.2 mmol g‐1 h‐1 and a remarkable apparent quantum efficiency of 25.1% at 450 nm, placing it among the state‐of‐the‐art performances in organic semiconductor photocatalysts. Furthermore, the versatility of the unsymmetric protonation approach has been successfully applied to four other photocatalysts, enhancing their photocatalytic performance by 39 to 533 times. These findings highlight the considerable potential of unsymmetric protonation induced symmetry breaking strategy in tailoring supramolecular photocatalysts for efficient solar‐to‐fuel production.

show abstract

Aerobic Oxidation of PMB Ethers to Carboxylic Acids

Zhang,

Qian

et al. 2024

Chemistry A European J

0

View full text Add to dashboard Cite

The first aerobic protocol of direct transformation of p‐methoxybenzyl (PMB) ethers to carboxylic acids efficiently with Fe(NO3)3•9H2O and TEMPO as catalysts at room temperature has been developed. The reaction accommodates C‐Br bond, terminal/non‐terminal C‐C triple bond, amide, cyano, nitro, ester, and trifluoromethyl groups, etc. Even highly selective oxidative deprotection of different benzylic PMB ethers has been realized. The reaction has been successfully applied to the total synthesis of natural product, (R)‐6‐hydroxy‐7,9‐octadecadiynoic acid, demonstrating the practicality of the method. Based on experimental studies, a possible mechanism involving oxygen‐stabilized benzylic cation has been proposed.

show abstract

Anthrazoline Photocatalyst for Promoting Esterification and Etherification Reactions via Photoredox/Nickel Dual Catalysis

Cited by 4 publications

References 64 publications

Enhancing Built‐in Electric Fields via Molecular Symmetry Modulation in Supramolecular Photocatalysts for Highly Efficient Photocatalytic Hydrogen Evolution

Enhancing Built‐in Electric Fields via Molecular Symmetry Modulation in Supramolecular Photocatalysts for Highly Efficient Photocatalytic Hydrogen Evolution

Enhancing Built‐in Electric Fields via Molecular Symmetry Modulation in Supramolecular Photocatalysts for Highly Efficient Photocatalytic Hydrogen Evolution

Aerobic Oxidation of PMB Ethers to Carboxylic Acids

Contact Info

Product

Resources

About