A π-Conjugated, Covalent Phosphinine Framework

Structural modularity of polymer frameworks is a key advantage of covalent organic polymers, however, only C, N, O, Si, and S have found their way into their building blocks so far. Here, the toolbox available to polymer and materials chemists is expanded by one additional nonmetal, phosphorus. Starting with a building block that contains a λ⁵ -phosphinine (C₅ P) moiety, a number of polymerization protocols are evaluated, finally obtaining a π-conjugated, covalent phosphinine-based framework (CPF-1) through Suzuki-Miyaura coupling. CPF-1 is a weakly porous polymer glass (72.4 m²  g^-1 BET at 77 K) with green fluorescence (λ_max =546 nm) and extremely high thermal stability. The polymer catalyzes hydrogen evolution from water under UV and visible light irradiation without the need for additional co-catalyst at a rate of 33.3 μmol h^-1  g^-1 . These results demonstrate for the first time the incorporation of the phosphinine motif into a complex polymer framework. Phosphinine-based frameworks show promising electronic and optical properties, which might spark future interest in their applications in light-emitting devices and heterogeneous catalysis.