Dynamic covalent chemistry, with its ability to correct synthetic dead-ends, allows for the synthesis of elaborate extended network materials in high yields. However, the limited number of reactions amenable to dynamic covalent chemistry necessarily confines the scope and functionality of materials synthesized. Here, we explore the dynamic and self-correcting nature of nucleophilic aromatic substitution (SNAr), using ortho-aryldithiols and ortho-aryldifluorides that condense to produce redox-active thianthrene units. We demonstrate the facile construction of two-, three- and four-point junctions by reaction between a dithiol nucleophile and three different model electrophiles that produces molecules with two, three and four thianthrene moieties, respectively, in excellent yields. The regioselectivity observed is driven by thermodynamics; other connections form under kinetic control. We also show that the same chemistry can be extended to the synthesis of novel ladder macrocycles and porous polymer networks with Brunauer–Emmett–Teller surface area of up to 813 m2 g−1.
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This work was supported by an Abdul Latif Jameel World Water and Food Security Lab (J-WAFS) Seed Grant. W.J.O. is indebted to the Agency for Science, Technology and Research (A*STAR), Singapore, for a graduate scholarship. The authors thank M. He for discussions and XPS measurements, B. Yoon for SEM measurements, R. Cook and A. Leshinsky for MALDI measurements, R. G. Griffin and D. Banks for ssNMR measurements, and I. Jeon for X-ray diffraction measurements.
The authors declare no competing interests.
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Ong, W.J., Swager, T.M. Dynamic self-correcting nucleophilic aromatic substitution. Nature Chem 10, 1023–1030 (2018). https://doi.org/10.1038/s41557-018-0122-8
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