A two‐step topotactic pathway for the preparation of phosphabenzene‐based porous organic polymers (POPs) under metal‐free conditions was achieved without the use of unstable phosphorus‐based monomers. This synthetic route allows additional functionalities to be introduced into the porous polymer framework with ease.
Significance and Impact
This work opens the door to the rational design and synthesis of porous organic phosphorine-based polymers with applications in gas separation and metal-based heterogeneous catalysis.
- Phosphabenzene‐functionalized POPs were prepared by synthesizing pyrylium‐functionalized POPs by a BF3⋅Et2O‐catalyzed condensation reaction and subsequent transformation of the pyrylium groups into phosphabenzene groups with P(Me3Si)3.
- Partially fluorinated polmers (F-Phos-POPs) are obtained with surface areas of up to 591 m2 g-1.
- After coordination with Ru species, a Ru/F-Phos-POPs catalyst exhibits superior efficiency in the formylation of amines using a CO2/H2 mixture.
Z. Yang, H. Chen, B. Li, W. Guo, K. Jie, Y. Sun, D. Jiang, I. Popovs and S. Dai Topotactically From Pyrylium to Phosphabenzene-Functionalized Porous Organic Polymers: Efficient Ligands in CO2 Conversion. Angew. Chem. Int. Ed. 2019, 58, 13763 –13767. DOI: 10.1002/anie.201907015