2D sp2 Carbon-Conjugated Covalent Organic Framework with Pyrene-Tethered TEMPO Intercalation for Photocatalytic Aerobic Oxidation of Sulfides into Sulfoxides

作者：Shi, Ji-Long; Feng, Keyu; Hao, Huimin; Ku, Calvin; Sit, Patrick H-L; Teoh, Wey Yang^*; Lang, Xianjun^*

来源：Solar RRL, 2022, 6(1): 2100608.

DOI：10.1002/solr.202100608

• covalent organic frameworks
• oxidation of sulfides
• photocatalysis
• red LEDs
• pi-pi
• stacking

The 2D covalent organic frameworks (COFs) offer many 2D planes which are suitable for pi-pi stacking interactions with other conjugated molecules. To improve the photocatalytic performance of COFs, the synthesis of a pyrene-tethered 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO) derivative cocatalyst is hereby described. The pyrene end of the cocatalyst is intercalated in between the layers of the 2D sp(2) carbon-conjugated porphyrin covalent organic framework (Por-sp(2)c-COF) via pi-pi stacking interactions evidenced by theoretical and experimental studies. The immobilization of pyrene-tethered TEMPO significantly enhances both the efficiency of photoinduced hole transfer and the stability of Por-sp(2)c-COF for the selective aerobic oxidation of a series of sulfides to sulfoxides under the irradiation of 623 nm red LEDs. This work highlights the merit of pi-pi stacking as a facile and efficient approach of immobilizing hole transfer cocatalysts without disrupting the physiochemical properties of the 2D COF photocatalyst.

• 单位
  武汉大学