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SuFExable polymers with helical structures derived from thionyl tetrafluoride


Sulfur(vi) fluoride exchange (SuFEx) is a category of click chemistry that enables covalent linking of modular units through sulfur(vi) connective hubs. The efficiency of SuFEx and the stability of the resulting bonds have led to polymer chemistry applications. Now, we report the SuFEx click chemistry synthesis of several structurally diverse SOF4-derived copolymers based on the polymerization of bis(iminosulfur oxydifluorides) and bis(aryl silyl ethers). This polymer class presents two key characteristics. First, the [–N=S(=O)F–O–] polymer backbone linkages are themselves SuFExable and undergo precise SuFEx-based post-modification with phenols or amines to yield branched functional polymers. Second, studies of individual polymer chains of several of these new materials indicate helical polymer structures. The robust nature of SuFEx click chemistry offers the potential for post-polymerization modification, enabling the synthesis of materials with control over composition and conformation.

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Fig. 1: SuFEx click chemistry for polymer synthesis.
Fig. 2: Kinetic profile of the polymerization of 1-1 (1 mmol) and 2-1 (1 mmol) (0.5 M in NMP, 3 mol% DBU).
Fig. 3: Post-polymerization modification of polymer 3-1 using sequential SuFEx and CuAAC click chemistry.
Fig. 4: The multidimensional connectivity of the S(vi) hubs: detailed structure studies.
Fig. 5: Substitution of S–F bond of optically pure sulfurofluoridoimidate in the presence of BEMP, racemization experiment for sulfurofluoridoimidate in the presence of DBU and reactive selectivity of iminosulfur oxydifluoride with aryl silyl ether.

Data availability

Data supporting the findings of this study are available within the Article and its Supplementary Information. Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition no. CCDC 2026570 [(R)-(−)-16]. Copies of the data can be obtained free of charge via Source data are provided with this paper.


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We acknowledge financial support from the National Science Foundation (CHE-1610987 to K.B.S.), the NIH (R35GM139643 to P.W.), the ARC for Supporting Future Fellowship FT170100156 (J.M.), the Guangdong Natural Science Funds for Distinguished Young Scholar (2018B030306018 to S.L.), the Program for Guangdong Introducing Innovative and Entrepreneurial Teams (2017ZT07C069 to S.L.) and the Pearl River Talent Recruitment Program (2019QN01L111 to S.L.), the National Science Foundation of China (#21871208 to H.Z. and 21971260 to S.L.), King Abdulaziz University (H.D. and H.Z.), and Basic Research Project of leading technology in Jiangsu Province (BK20202012 to J.L.). Part of the work was carried out as a user project at the Molecular Foundry, supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231. We thank L. Liang (Shanxi University) for assistance with X-ray single-crystal structural analyses and S. Ruggeri and B. van Lagen (Wageningen University) for detailed AFM analysis. We are grateful to J.R. Cappiello for proofreading and advice on the manuscript.

Author information




K.B.S., J.M. and H.Z. supervised the work. S.L., K.B.S., P.W., J.L. and J.M. conceived and designed the syntheses of the SOF4-derived polymers. S.L., G.L., B.G., S.P.P., X.C. and H.K. performed the synthesis and characterization of the polymers. F.Z., L.M.K., Y.L. and J.L. collected and analysed the DSC and TGA data for all polymers. F.Z. collected the XRD data. S.P.P. performed molecular modelling, AFM and scanning Auger experiments. H.D. performed the SEM and TEM experiments. D.-D.L. collected the circular dichroism data. S.L., H.Z., K.B.S. and J.M. contributed to the preparation of the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Suhua Li, Peng Wu, Han Zuilhof, John Moses or K. Barry Sharpless.

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Competing interests

K.B.S., P.W., S.L. and B.G. are named as inventors on a patent applicant filed by The Scripps Research Institute (provisional patent application US62/427,489, filed on 29 November 2016, and international patent application no. PCT/US2017/063746).

Additional information

Peer review information Nature Chemistry thanks Jason Locklin, Jia Niu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–17, Supplementary procedures and all characterization data, NMR spectra, HPLC chromatogram and Supplementary Table 1.

Supplementary Data

CIF file with structure factors.

Source data

Source Data Fig. 2

Transformation data of –N=SOF2 at the indicated times and calculation details.

Source Data Fig. 3

Intensity (a.u.) data (11 groups for water content vol% of 0–99%) from wavelength 370 nm to 570 nm.

Source Data Fig. 4

Figure 4c AFM profile.

Source Data Fig. 4

Figure 4f Amplitude profile.

Source Data Fig. 4

Figure 4g FFT amplitude.

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Li, S., Li, G., Gao, B. et al. SuFExable polymers with helical structures derived from thionyl tetrafluoride. Nat. Chem. 13, 858–867 (2021).

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