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. 2025 Jun 6;15(12):10736-10745.
doi: 10.1021/acscatal.5c02173. eCollection 2025 Jun 20.

Nile Red-Based Covalent Organic Framework as a Photocatalyst for C-H Bond Functionalization

Marta Gordo-Lozano  1 , Diego G Matesanz  2   3 , Marcos Martínez-Fernández  1 , Pedro Almendros  4 , Emiliano Martínez-Periñán  5 , José L Segura  1 , Sara Cembellín  2   3
Affiliations

Nile Red-Based Covalent Organic Framework as a Photocatalyst for C-H Bond Functionalization

Marta Gordo-Lozano et al. ACS Catal. .

Abstract

The search for efficient photocatalysts based on covalent organic frameworks (COFs) is an area of increasing interest. However, the development of these heterogeneous photocatalysts is hindered by the symmetry restrictions of the linkers used to construct these materials. Herein, we report the straightforward synthesis of an imine-based 2D-COF, NR 0.17 -COF, which incorporates a Nile Red (NR) unit via postmodification with a NR-alkyne scaffold. This framework exhibits remarkable photocatalytic activity across various photoredox-catalyzed C-H functionalization reactions, demonstrating the ability to directly functionalize prevalent bonds in organic molecules under mild conditions and with low-energy light. The NR 0.17 -COF showcases notable versatility, effectively generating aryl, sulfur, and nitrogen radicals from different radical precursors while maintaining good functional group tolerance. Moreover, our heterogeneous photocatalyst outperforms traditional homogeneous systems by addressing critical challenges such as scalability and recyclability, allowing for a 10-fold increase in the reaction scale and enabling recovery and reuse up to six times. This advancement significantly enhances the potential of COF postsynthetic modification for practical applications in organic synthesis, which marks a substantial step forward in photocatalytic technology.

Keywords: COF; C−H functionalization; Nile Red; heterogeneous catalysis; photocatalysis.

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Figures

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1. (a–c) Overview of This Work
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2. Synthesis of NR-Alk
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3. Synthesis of NR0.17-COF
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(A) FTIR spectra of Azide 0.17 -COF (black), NR-Alk (blue), and NR 0.17 -COF (magenta). (B) PXRD patterns of Azide 0.17 -COF (black) and NR 0.17 -COF (magenta). The inset shows a magnification in the 5.4–30° range. (C) N2 sorption isotherms of Azide 0.17 -COF (black) and NR 0.17 -COF (magenta). Empty symbols represent the desorption branches. (D) Pore size distribution of Azide 0.17 -COF (black) and NR 0.17 -COF (magenta).
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(A) SEM micrograph of NR 0.17 -COF. (B) TEM micrograph of NR 0.17 -COF. (C) UV–vis spectra of the compounds under study in a THF/H2O (7/3) mixture.
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4. Substrate Scope of the Light-Mediated Arylation of Heteroarenes with Aryldiazonium Salts
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5. (a–c) NR0.17-COF as a Photocatalyst in Other Light-Mediated C–H Functionalization Reactions
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(A) Scaled-up standard reaction using NR 0.17 -COF. (B) Recyclability of NR 0.17 -COF in the standard reaction. (C) Comparison of FTIR spectra of NR 0.17 -COF before (red) and after (black) catalysis. (D) Comparison of PXRD patterns of NR 0.17 -COF before (black) and after (magenta) catalysis. (E) Kinetic profiles for the standard reaction with different catalysts. (F) “Light/dark” experiments for the standard reaction using NR 0.17 -COF.
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Cyclic voltammograms recorded at modified glassy carbon with carbon black (black) and with NR 0.17 -COF/carbon black (red) and Azide 0.17 -COF/carbon black (blue) in a 0.1 M TBAP/acetonitrile solution in the absence of O2. Cyclic voltammograms were recorded at modified glassy carbon with carbon black in the presence of 1 mg/mL NR-Alk (green) in 0.1 M TBAP/acetonitrile solution in the absence of O2.
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6. Plausible Mechanism for Light-Mediated Arylation of Heteroarenes with NR0.17-COF as a Catalyst
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