Hyper-Cross-Linked Porous Polymer Featuring B–N Covalent Bonds (HCP-BNs): A Stable and Efficient Metal-Free Heterogeneous Photocatalyst

[Image: see text] The first example of a porous polymer containing B–N covalent bonds, prepared from a tetraphene B–N monomer and biphenyl as a comonomer, is reported. It was prepared using the solvent knitting strategy, which allows the connection between the aromatic rings of the two monomers through methylene groups provided by an external cross-linking agent. The new polymer exhibited micromeso porosity with an S(BET) of 612 m(2)/g, high thermal stability, and potential properties as a heterogeneous photocatalyst, since it is very active in the aza-Henry coupling reaction (>98% of conversion and selectivity). After the first run, the catalyst improves its photocatalytic activity, shortening the reaction time to only 2 h and maintaining this activity in successive runs. The presence of a radical in this structure that remains stable with successive runs makes it a new type of material with potential applications as a highly stable and efficient photocatalyst.