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[Display omitted] • Thiazolo[5,4- d ]thiazole (TzTz) is employed as the linkage to synthesize CMPs. • The TzTz-linked CMPs are thoroughly characterized. • TzTz-CMP-3 displays excellent photocatalytic activity for selective aerobic oxidation. • The photocatalytic properties of TzTz-linked CMPs could be tailored by molecular symmetry. • TzTz-CMP-3 with unprecedent activity is uncovered for the formation of sulfoxides. Developing selective formation of sulfoxides by aerobic oxidation of sulfides over highly efficient visible-light photocatalysts is an essential but challenging task. Herein, a conjugated microporous polymer (CMP) photocatalyst with the desired linkage thiazolo[5,4‑ d ]thiazole (TzTz) is presented to undertake this task. Remarkably, a catalyst-free solvothermal process afforded TzTz-CMP-3 from tetra(4-formylphenyl)-benzene and dithiooxamide. The photocatalytic activity of TzTz-CMP-3 is demonstrated with the blue light-powered selective formation of sulfoxides by aerobic oxidation of sulfides. A wide range of sulfoxides can be effectively formed by oxidation of sulfides with excellent product selectivities (up to 99 %) over the TzTz-CMP-3 photocatalyst. The more symmetric π-conjugated aromatic ring of TzTz-CMP-3 endows it with more favorable activity than the less symmetric ones. This work underscores the symmetry of building blocks for CMPs for selective photocatalytic formation of valuable organic molecules. [ABSTRACT FROM AUTHOR]

The selective aerobic oxidation of benzylamine by cooperative ARS-TNTs photocatalysis with TEMPO+BF 4 −. [Display omitted] • Anatase TNTs deliver outstanding photocatalytic activity. • ARS binds with TNTs through surface hydroxyl sites. • Electron transfer occurs smoothly between ARS-TNTs and TEMPO+BF 4 −. • With increased polarity, TEMPO+BF 4 − can increase cooperative photocatalysis. • Green light-driven selective aerobic oxidation of amines has been achieved. Visible light photocatalysis could offer an eco-friendly alternative for selective transformation of organic molecules. Herein, a cooperative system is created with alizarin red S (ARS), TiO 2 nanotubes (TNTs), and an extra redox mediator. The electron transfer between oxidatively quenched ARS-TNTs and the redox mediator is the key to secure cooperative photocatalysis. The selective aerobic oxidation of primary and secondary amines was constructed by cooperative photocatalysis of ARS-TNTs with 2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate (TEMPO+BF 4 −) driven by green light. Specifically, the activity of anatase TNTs could reach about 2.2 times that of the P25 (Aeroxide P25) TiO 2 precursor. Due to increased polarity, TEMPO+BF 4 − serves more efficiently for electron transfer than (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO), conferring above 1.5 times of activity that of TEMPO for the selective aerobic conversion of amines. This work features the potential of designing redox mediators in amplifying cooperative photocatalysis driven by visible light. [ABSTRACT FROM AUTHOR]