Site‐Selective Synthesis and Concurrent Immobilization of Imine‐Based Covalent Organic Frameworks on Electrodes Using an Electrogenerated Acid

• Published in: Angewandte Chemie International Edition Vol. 62; no. 40; pp. e202307343 - n/a
• Main Authors: Shirokura, Tomoki, Hirohata, Tomoki, Sato, Kosuke, Villani, Elena, Sekiya, Kazuyasu, Chien, Yu‐An, Kurioka, Tomoyuki, Hifumi, Ryoyu, Hattori, Yoshiyuki, Sone, Masato, Tomita, Ikuyoshi, Inagi, Shinsuke
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 02.10.2023
• Edition: International ed. in English
• Subjects: Aldehydes; Catalysts; Covalent Organic Frameworks; Electrochemical oxidation; Electrochemistry; Electrode; Electrodes; Electrogenerated Acid; Film thickness; Imine Bond; Immobilization; Monomers; Organic solvents; Porous Film; Porous materials; Production methods; Substrates; Synthesis; Electrogenerated Acid; Electrode; Porous Film; Covalent Organic Frameworks; Imine Bond
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202307343

Imine‐based covalent organic frameworks (COFs) are crystalline porous materials with prospective uses in various devices. However, general bulk synthetic methods usually produce COFs as powders that are insoluble in most of the common organic solvents, arising challenges for the subsequent molding and fixing of these materials on substrates. Here, we report a novel synthetic methodology that utilizes an electrogenerated acid (EGA), which is produced at an electrode surface by electrochemical oxidation of a suitable precursor, acting as an effective Brønsted acid catalyst for imine bond formation from the corresponding amine and aldehyde monomers. Simultaneously, it provides the corresponding COF film deposited on the electrode surface. The COF structures obtained with this method exhibited high crystallinities and porosities, and the film thickness could be controlled. Furthermore, such process was applied for the synthesis of various imine‐based COFs, including a three‐dimensional (3D) COF structure. Here, we report a novel synthetic methodology for covalent organic frameworks (COFs) that utilizes an electrogenerated acid (EGA), which is produced at an electrode surface by electrochemical oxidation of a precursor, acting as an effective Brønsted acid catalyst for imine bond formation from amine and aldehyde monomers. Simultaneously, it provides the corresponding COF film deposited on the electrode surface with high crystallinity and porosity.