Covalent Scrambling in Porous Polyarylthioethers through a Stepwise SNAr for Tunable Bandgap and Porosity

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, inexpe...

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Bibliographic Details
Published inAngewandte Chemie International Edition Vol. 62; no. 28
Main Authors Kim, Doyun, Nguyen, Thien S., Lee, Hyejeong, Bayarkhuu, Bolormaa, Rozyyev, Vepa, Byun, Jeehye, Li, Sheng, Yavuz, Cafer T.
Format Journal Article
LanguageEnglish
Published Weinheim Wiley Subscription Services, Inc 10.07.2023
EditionInternational ed. in English
Subjects
Aromatic compounds
Catalysis
Energy gap
Functional groups
Mercury
Mercury (metal)
Microporosity
Pollutant removal
Polyarylthioethers
Polycondensation
Polymers
Porosity
Porous Polymers
Regioselectivity
Selective Adsorption
Sodium sulfide
Sulfides
Sulfur
Temperature dependence
Thiols
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Summary: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. A conventional polycondensation reaction can provide the simplest route to generating porous poly(aryl thioether)s. Controlling the temperature orients the reaction toward the regioselective multi‐substitution of aryl fluorides, demonstrating a stepwise change in the porosity and optical band gap of the poly(aryl thioether)s.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202304378