Toward Two‐Dimensional π‐Conjugated Covalent Organic Radical Frameworks. Issue 27 (30th May 2018)

• Record Type: Journal Article
• Authors: Wu, Shaofei; Li, Minchan; Phan, Hoa; Wang, Dingguan; Herng, Tun Seng; Ding, Jun; Lu, Zhouguang; Wu, Jishan
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 27(2018)
• Page Start: 8007
• Page End: 8011
• Publication Date: 2018-05-30
• Subjects: covalent organic frameworks -- materials science -- oxygen reduction reaction -- radicals -- structure elucidation; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201801998
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Reported is the synthesis, characterization, and material properties of the first π‐conjugated two‐dimensional covalent organic radical framework (CORF), PTM‐CORF, based on the stable polychlorotriphenylmethyl (PTM) radical. The covalent organic framework (COF) precursor (PTM‐H‐COF ) was first synthesized by liquid/liquid interfacial acetylenic homocoupling of a triethynylpolychlorotriphenylmethane monomer, and showed crystalline features with a hexagonal diffraction pattern matching that of A‐B‐C stacking. Subsequent deprotonation and oxidation of the PTM units in PTM‐H‐COF gave PTM‐CORF . Magnetic measurements revealed that the neighboring PTM radicals in the PTM‐CORF are anti‐ferromagnetically coupled each other, with a moderate exchange interaction ( J =−375 cm −1 ). The PTM‐CORF has a small energy gap (ca. 0.88 eV) and a low‐lying LUMO energy level (−4.72 eV), and exhibits high electrocatalytic activity and durability toward the oxygen reduction reaction. Abstract : Ahead of the CORF : A π‐conjugated 2D covalent organic radical framework (CORF), based on stable polychlorotriphenylmethyl radicals, was prepared. It shows moderate anti‐ferromagnetic spin–spin exchange interactions, a small energy gap, and a low‐lying LUMO energy level. Electrochemical analysis of the CORF exhibited a high electrocatalytic activity and durability toward the oxygen reduction reaction.