Similar Publications

A dual-engineered covalent organic framework with charge-oxygen synergy promotes photocatalytic dipolar [3 + 2] cycloaddition.

Chem Sci

August 2025

College of Chemistry and Materials Science, Key Laboratory of Chemical Biology of Hebei Province, Hebei Research Center of the Basic Discipline of Synthetic Chemistry, Institute of Life Science and Green Development Hebei University Baoding Hebei 071002 P. R. China

The photocatalytic oxidative dipolar [3 + 2] cycloaddition reaction is a promising green approach for producing pyrrolo[2,1-]isoquinolines. However, developing sustainable cycloaddition methods with heterogeneous photocatalysts is still in its infancy, largely owing to their low reactivity and photostability. Herein, we propose a charge-oxygen synergy strategy through a dual-engineered covalent organic framework (COF) by integrating π-spacers with donor-acceptor motifs to promote intermolecular cycloaddition.

View Article and Find Full Text PDF

Polytantalotungstates Stabilized Iron Catalysts for Carbonylation of Benzylic C-H Bonds.

Inorg Chem

September 2025

Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Molecular Sciences, Henan University, Kaifeng, Henan 475004, China.

Selective oxidation of benzylic C(sp)-H bonds to ketones is critical to the production of fine chemicals but typically requires toxic/precious metal catalysts under harsh conditions. While iron-based complexes have recently served as catalysts for photocatalytic C-H bond activation, most systems operate via homogeneous catalysis. Developing a light-driven strategy under visible light with O as an oxidant is of major importance.

View Article and Find Full Text PDF

Ultralong-Lived Excitons in Metallo-Quinoline-Incorporated Covalent Organic Frameworks Promote Photoreductive Cross-Coupling.

Angew Chem Int Ed Engl

September 2025

College of Polymer Science and Engineering, State Key Laboratory of Advanced Polymer Materials, Sichuan University, Chengdu, 610065, P.R. China.

Designing long-lived excitons in photocatalysts is crucial for efficient charge separation. However, most of the current organic photocatalysts are characterized by a relatively short exciton lifetime within the range of picoseconds due to localized excitons with large binding energies. Herein, we report the design of ultralong-lived excitons with a lifetime exceeding 8000 ps by constructing metallo-quinoline-incorporated covalent organic frameworks (COFs).

View Article and Find Full Text PDF

Quasi-Homogeneous Photocatalytic C─H Functionalization Enabled by Donor-Acceptor Microporous Polymer Aerogels Featuring Ultralong-Lived and Long-Range Excitons.

Angew Chem Int Ed Engl

September 2025

College of Polymer Science and Engineering, State Key Laboratory of Advanced Polymer Materials, Sichuan University, Chengdu, 610065, P.R. China.

Simultaneous promotion of charge and mass transportation between catalytic centers and reactants is crucial for photocatalysis but remains a substantial challenge on account of the widespread use of homogeneous or heterogeneous photocatalysts that suffer from sluggish reactant-diffusion kinetics or interfacial electron-transport resistance, respectively. Herein, we demonstrate the construction of conjugated microporous polymer aerogels as available quasi-homogeneous photocatalysts by integrating structural designability, which allows for the incorporation of electron-acceptor building blocks featuring ultralong-lived excitons as high-concentration local catalytic centers, and hierarchically porous gel networks that wrap solvent and reactants to provide a "single" reaction phase without interfacial resistance. A total of 18 samples of C─H functionalization reactions underpinned by four different mechanisms were screened to showcase the general applicability of the obtained aerogel photocatalysts, which achieved remarkable conversion efficiencies, gram-scale productivities, and recyclability.

View Article and Find Full Text PDF

While intricate designs have been implemented to transform noble-metal complexes and sophisticated organic molecules into reactive photocatalysts for the single-electron reduction of unactivated alkyl halides, the development of highly reducing photocatalytic systems based on earth-abundant metals is still in its early stages. Herein, we show that a simple terpyridine-ligated nickel(II) complex, integrated into an imine-linked covalent organic framework, can be readily reduced by photoexcited Hantzsch esters to produce a heterogeneous nickel(I) photocatalyst with a fairly low excited-state oxidation potential of approximately -3.5 V (referenced to the saturated calomel electrode).

View Article and Find Full Text PDF