Porous polymer catalysts possess the potential to combine the advantages of heterogeneous and homogeneous catalysis, namely, easy postreaction recycling and high dispersion of active sites. Here, we designed a -SO3H functionalized polyphenylene (PPhen) framework with purely sp2-hybridized carbons, which exhibited high activity in the hydration of alkynes including challenging aliphatic substrates such as 1-octyne. The superiority of the structure lies in its covalent crosslink in the xy-plane with a π-π stacking interaction between the planes, enabling simultaneously high swellability and porosity (653 m2·g-1). High acidic site density (2.12 mmol·g-1) was achieved under a mild sulfonation condition. Similar turnover frequencies (0.015 ± 0.001 min-1) were obtained regardless of acidic density and crosslink content, suggesting high accessibility for all active sites over PPhen. In addition, the substituted benzene groups can activate alkynes through a T-shape CH/π interaction, as indicated by the 8 and 16 cm-1 red shift of the alkyne C-H stretching peak for phenylacetylene and 1-octyne, respectively, in the infrared (IR) spectra. These advantages render PPhen-SO3H a promising candidate as a solid catalyst replacing the highly toxic liquid phase acids such as the mercury salt.
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