Visible light photocatalysis of covalent organic frameworks (COFs) has made significant progress in recent years. Benzotrithiophene (BTT), a planar, electron-rich building block, turns out to be foundational in assembling COFs in which the full π-conjugation of BTT is essential to facilitate electron transfer. Herein, a sp² carbon-conjugated COF, namely BTT-sp²c-COF, is assembled from benzo[1,2-b:3,4-b′:5,6-b″]trithiophene-2,5,8-tricarbaldehyde and [1,1′:4′,1″-terphenyl]-4,4″-dicarbonitrile towards photocatalysis. More importantly, TEMPO (2,2,6,6-tetramethylpiperidin-1-yl)oxyl, 1 mol%) could considerably accelerate the selective oxidation of organic sulfides with O₂ over BTT-sp²c-COF. TEMPO mediates hole transfer between BTT-sp²c-COF and organic sulfides, and O-atoms are incorporated into sulfoxides via an electron transfer pathway. Merging BTT-sp²c-COF photocatalysis with TEMPO generally applies to transforming organic sulfides into sulfoxides. This work implies the full π-conjugation of electron-rich building blocks into COFs is a viable strategy for selective visible light photocatalysis.

近年来，共价有机框架（COF）的可见光光催化取得了重大进展。苯并三噻吩 (BTT) 是一种平面、富含电子的结构单元，它是组装 COF 的基础，其中 BTT 的完整 π 共轭对于促进电子转移至关重要。本文中，sp ²碳共轭COF，即BTT-sp ² c-COF，由苯并[1,2-b:3,4-b':5,6-b”]三噻吩-2,5组装而成， 8-三甲醛和[1,1':4',1"-三联苯]-4,4"-二甲腈用于光催化。更重要的是，TEMPO (2,2,6,6-四甲基哌啶-1-基)氧基，1 mol%)可以显着加速BTT-sp ² c-COF上O _{2对有机硫化物的选择性氧化。}TEMPO 介导 BTT-sp 之间的空穴转移^{2 c-COF 和有机硫化物以及 O 原子}通过电子转移途径结合到亚砜中。将 BTT-sp ² c-COF 光催化与 TEMPO 相结合通常适用于将有机硫化物转化为亚砜。这项工作表明，将富电子结构单元完全π共轭结合成COF是选择性可见光光催化的可行策略。