Polyphosphonate covalent organic frameworks.

Xu, Ke; Oestreich, Robert; Haj Hassani Sohi, Takin; Lounasvuori, Mailis; Ruthes, Jean G A; Zorlu, Yunus; Michalski, Julia; Seiffert, Philipp et al. · Nat Commun · 2024

basic_science · Level V

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Abstract

Herein, we report polyphosphonate covalent organic frameworks (COFs) constructed via P-O-P linkages. The materials are synthesized via a single-step condensation reaction of the charge-assisted hydrogen-bonded organic framework, which is constructed from phenylphosphonic acid and 5,10,15,20-tetrakis[p-phenylphosphonic acid]porphyrin and is formed by simply heating its hydrogen-bonded precursor without using chemical reagents. Above 210 °C, it becomes an amorphous microporous polymeric structure due to the oligomerization of P-O-P bonds, which could be shown by constant-time solid-state double-quantum <sup>31</sup>P nuclear magnetic resonance experiments. The polyphosphonate COF exhibits good water and water vapor stability during the gas sorption measurements, and electrochemical stability in 0.5 M Na<sub>2</sub>SO<sub>4</sub> electrolyte in water. The reported family of COFs fills a significant gap in the literature by providing stable microporous COFs suitable for use in water and electrolytes. Additionally, we provide a sustainable synthesis route for the COF synthesis. The narrow pores of the COF effectively capture CO<sub>2</sub>.