Toward Two-Dimensional π-Conjugated Covalent Organic Radical Frameworks

被引：166

作者：

Wu, Shaofei ^{[1
]}

Li, Minchan ^{[2
]}

Phan, Hoa ^{[1
]}

Wang, Dingguan ^{[1
]}

Herng, Tun Seng ^{[3
]}

Ding, Jun ^{[3
]}

Lu, Zhouguang ^{[2
]}

Wu, Jishan ^{[1
]}

机构：

[1] Natl Univ Singapore, Dept Chem, 3 Sci Dr 3, Singapore 117543, Singapore

[2] Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen 518055, Peoples R China

[3] Natl Univ Singapore, Dept Mat Sci & Engn, Singapore 119260, Singapore

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 27期

关键词：

covalent organic frameworks; materials science; oxygen reduction reaction; radicals; structure elucidation; CRYSTALLINE; GRAPHDIYNE; REDUCTION; GRAPHENE; DESIGN;

D O I：

10.1002/anie.201801998

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Reported is the synthesis, characterization, and material properties of the first pi-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.

引用

页码：8007 / 8011

页数：5

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