Triazine-based two dimensional porous materials for visible light-mediated oxidation of sulfides to sulfoxides with...

Recently, triazine-based two dimensional (2D) porous materials have received increasing attention in photocatalysis. Herein, CTF-1, a covalent triazine framework, was adopted as the blueprint for designing a 2D bespoke photocatalyst. The thiazolo[5,4-d]thiazole (TzTz) linkage was inserted into the framework of CTF-1, affording TzTz-TA, which belongs to conjugated microporous polymers (CMPs). Rather than the direct insertion via the challenging CH activation, TzTz-TA was assembled from 2,4,6-tris(4-formylphenyl)-1,3,5-triazine and dithiooxamide, in which TzTz was formed in situ by a process of catalyst-free solvothermal condensation. Both CTF-1 and TzTz-TA had similar energy gaps (E_g), photocurrents, and charge carrier lifetimes, in line with the similar molecular underpinnings. However, the reduction potential of TzTz-TA is less negative than that of CTF-1 due to the insertion of TzTz linkage, in a more appropriate position for activating O₂ to superoxide (O₂^•-). In return, blue light-mediated oxidation of sulfides to sulfoxides with O₂ over TzTz-TA was accomplished with significantly superior conversions to those over CTF-1. Intriguingly, extensive sulfides could be oxidized to corresponding sulfoxides with outstanding recycling stability of TzTz-TA. Notably, attendance of an induction period was observed during TzTz-TA photocatalysis. This work highlights the vast potential of designing triazine-based porous materials to meet the tailor-made demands, such as the oxidative transformation of organic molecules with O₂.