Pyrene-Based D-A Molecules as Efficient Heterogeneous Catalysts for Visible-Light-Induced Aerobic Organic Transformations.

In this work, an efficient visible light promoted aerobic dehydro-coupling of amines, oxidation of thioethers and hydroxylation of arylboronic acids under benign conditions by using pyrene-based donor-acceptor (D-A) conjugated organic molecules was described. Donor-acceptor structure influences their π-conjugation and band gap a lot, and thereby enhances their visible light absorption ability, single electron transfer and oxidative behaviors. Alkynyl units in PS-IV play a crucial role in the catalyst which could serve as electron transferring bridge to strengthen electron delocalization, thus facilitating the single electron transfer from photosensitizer to substrates, and making it an efficient ⋅O generator. While PS-III without alkynyl units tends to produce O . Therefore, these molecules can serve as efficient catalysts for different kinds of visible-light-induced aerobic organic reactions. More importantly, the simply structured molecule is insoluble and stable in various solvents, and thus could be recycled as heterogeneous catalyst for many rounds with slight catalytic activity degradation. Besides, large scale (1 mol) reaction of benzylamine coupling proceeded smoothly under the standard conditions.