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Toward Two‐Dimensional π‐Conjugated Covalent Organic Radical Frameworks
Author(s) -
Wu Shaofei,
Li Minchan,
Phan Hoa,
Wang Dingguan,
Herng Tun Seng,
Ding Jun,
Lu Zhouguang,
Wu Jishan
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201801998
Subject(s) - stacking , conjugated system , covalent bond , monomer , radical , covalent organic framework , deprotonation , chemistry , homo/lumo , photochemistry , materials science , polymer chemistry , polymer , organic chemistry , molecule , ion
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.