Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu, Daejeon, 34141, Republic of Korea.
Advanced Membranes and Porous Materials Center (AMPMC), Physical Science and Engineering (PSE), King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia.
Angew Chem Int Ed Engl. 2023 Jul 10;62(28):e202304378. doi: 10.1002/anie.202304378. Epub 2023 May 5.
Porous poly(aryl thioether)s offer stability and electronic tunability by robust sulfur-aryl conjugated architecture, but synthetic access is hindered due to limited control over the nucleophilic nature of sulfides and the air sensitivity of aromatic thiols. Here, we report a simple, one-pot, inexpensive, regioselective synthesis of highly porous poly(aryl thioether)s through polycondensation of perfluoroaromatic compounds with sodium sulfide. The unprecedented temperature-dependent para-directing formation of thioether linkages leads to a stepwise transition of the polymer extension into a network, thereby allowing fine control of the porosity and optical band gaps. The obtained porous organic polymers with ultra-microporosity (<1 nm) and sulfur as the surface functional groups show size-dependent separation of organic micropollutants and selective removal of mercury ions from water. Our findings offer easy access to poly(aryl thioether)s with accessible sulfur functionalities and higher complexity, which will help in realizing advanced synthetic designs in applications such as adsorption, (photo)catalysis, and (opto)electronics.
多孔聚（芳基硫醚）通过坚固的硫-芳基共轭结构提供稳定性和电子可调性，但由于对硫化物的亲核性和芳基硫醇的空气敏感性的控制有限，其合成受到阻碍。在这里，我们通过全氟芳烃化合物与硫化钠的缩聚反应，报道了一种简单、一锅、廉价、区域选择性合成高度多孔聚（芳基硫醚）的方法。前所未有的硫醚键形成的温度依赖性对位导向导致聚合物延伸成网络的逐步转变，从而可以精细控制孔隙率和光学带隙。具有超微孔（<1nm）和硫作为表面官能团的所得多孔有机聚合物对有机微污染物表现出尺寸依赖性分离和从水中选择性去除汞离子。我们的发现为具有可及的硫官能团和更高复杂性的聚（芳基硫醚）提供了便捷的途径，这将有助于在吸附、（光）催化和（光电）等应用中实现先进的合成设计。
