Extending the 2D conjugated microporous polymers linked by thiazolo[5,4-]thiazole for green light-driven selective aerobic oxidation of amines

Conjugated microporous polymers (CMPs) have emerged as multifaceted photocatalysts whose properties can be precisely tuned at the molecular level. Herein, donor-π-acceptor (D-π-A) type CMPs linked by the electron-deficient thiazolo[5,4- d ]thiazole (TzTz, i.e. the acceptor) were designed by extending the donor from benzene to pyrene to broaden the visible light activity. Subsequently, two-dimensional (2D) CMPs, TzTz-CMP-Be and TzTz-CMP-Py, were constructed via a solvothermal process. Notably, the more extended π-conjugation and planar pyrene bestow upon TzTz-CMP-Py with broader absorption of visible light and higher efficiency of charge transfer than TzTz-CMP-Be. Significantly, TzTz-CMP-Py outperformed TzTz-CMP-Be in the green light-driven selective aerobic oxidation of amines. Remarkable photocatalytic performance was observed in converting a wealth of primary and secondary amines to corresponding imines with molecular oxygen (O 2 ) over TzTz-CMP-Py. This work suggests that CMPs can be rationally designed for extensive visible light-driven selective organic transformations. With pyrene as the donor, a conjugated microporous polymer linked by thiazolo[5,4- d ]thiazole (TzTz) is with notable green light-driven performance in the selective aerobic oxidation of benzyl amines.