Affiliation: | 1. Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu, Daejeon, 34141 Republic of Korea;2. 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 KAUST Catalysis Center (KCC), Physical Science & Engineering (PSE), King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900 Saudi Arabia;3. Water Cycle Research Center, Korea Institute of Science and Technology (KIST), Seoul, 02792 Republic of Korea;4. Pritzker School of Molecular Engineering, The University of Chicago, 5640 South Ellis Avenue, Chicago, IL 60637 USA;5. 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 |
Abstract: | 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. |