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 (λmax =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.

Bundesanstalt für Materialforschung und prüfung Unter den Eichen 87 12205 Berlin Germany

College of Polymer Science and Engineering State Key Laboratory of Polymer Materials Engineering Sichuan University Chengdu 610065 P R China

Department of Chemistry Humboldt Universität zu Berlin Brook Taylor Str 2 12489 Berlin Germany

Division Biophotonics Federal Institute for Materials Research and Testing Richard Willstätter Straße 11 12489 Berlin Germany

Institute of Chemistry and Biochemistry Free University of Berlin Takustrasse 3 14195 Berlin Germany

Institute of Organic Chemistry and Biochemistry of the CAS Flemingovo nám 2 166 10 Prague Czech Republic

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