Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489, Berlin, Germany.
Institute of Organic Chemistry and Biochemistry of the CAS, Flemingovo nám. 2, 166 10, Prague, Czech Republic.
Chemistry. 2019 Sep 20;25(53):12342-12348. doi: 10.1002/chem.201900281. Epub 2019 Aug 13.
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 λ -phosphinine (C 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 m g BET at 77 K) with green fluorescence (λ =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 g . 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.
聚合物框架的结构模块化是共价有机聚合物的一个关键优势，然而，迄今为止，只有 C、N、O、Si 和 S 被纳入其构建块中。在这里，通过引入一种额外的非金属元素磷，扩展了聚合物和材料化学家可用的工具包。从含有 λ -磷杂环戊烯（C P）部分的构建块开始，评估了许多聚合方案，最终通过 Suzuki-Miyaura 偶联得到了π共轭的共价磷杂环戊烯基框架（CPF-1）。CPF-1 是一种具有弱多孔性的聚合物玻璃（77 K 时 BET 为 72.4 m g），具有绿色荧光（λ =546 nm）和极高的热稳定性。该聚合物在紫外光和可见光照射下无需额外助催化剂即可催化水的析氢反应，其速率为 33.3 μmol h g 。这些结果首次证明了磷杂环戊烯基结构单元被纳入复杂聚合物框架中。基于磷杂环戊烯的框架表现出有前景的电子和光学性质，这可能激发未来在发光器件和多相催化中的应用兴趣。
