Single-Crystal Polycationic Polymers Obtained by Single-Crystal-to-Single-Crystal Photopolymerization

Qing Hui Guo, Manping Jia, Zhichang Liu, Yunyan Qiu, Hongliang Chen, Dengke Shen, Xuan Zhang, Qing Tu, Matthew R. Ryder, Haoyuan Chen, Peng Li, Yaobin Xu, Penghao Li, Zhijie Chen, Gajendra S. Shekhawat, Vinayak P. Dravid, Randall Q. Snurr, Douglas Philp, Andrew C.H. Sue, Omar K. FarhaMarco Rolandi, J. Fraser Stoddart*

*Corresponding author for this work

Research output: Contribution to journalArticle

Abstract

The efficient preparation of single-crystalline ionic polymers and fundamental understanding of their structure-property relationships at the molecular level remains a challenge in chemistry and materials science. Here, we describe the single-crystal structure of a highly ordered polycationic polymer (polyelectrolyte) and its proton conductivity. The polyelectrolyte single crystals can be prepared on a gram-scale in quantitative yield, by taking advantage of an ultraviolet/sunlight-induced topochemical polymerization, from a tricationic monomer- A self-complementary building block possessing a preorganized conformation. A single-crystal-to-single-crystal photopolymerization was revealed unambiguously by in situ single-crystal X-ray diffraction analysis, which was also employed to follow the progression of molecular structure from the monomer, to a partially polymerized intermediate, and, finally, to the polymer itself. Collinear polymer chains are held together tightly by multiple Coulombic interactions involving counterions to form two-dimensional lamellar sheets (1 nm in height) with sub-nanometer pores (5 Å). The polymer is extremely stable under 254 nm light irradiation and high temperature (above 500 K). The extraordinary mechanical strength and environmental stability-in combination with its impressive proton conductivity (âˆ3 × 10-4 S cm-1)-endow the polymer with potential applications as a robust proton-conducting material. By marrying supramolecular chemistry with macromolecular science, the outcome represents a major step toward the controlled synthesis of single-crystalline polyelectrolyte materials with perfect tacticity.

Original languageEnglish (US)
Pages (from-to)6180-6187
Number of pages8
JournalJournal of the American Chemical Society
Volume142
Issue number13
DOIs
StatePublished - Apr 1 2020

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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    Guo, Q. H., Jia, M., Liu, Z., Qiu, Y., Chen, H., Shen, D., Zhang, X., Tu, Q., Ryder, M. R., Chen, H., Li, P., Xu, Y., Li, P., Chen, Z., Shekhawat, G. S., Dravid, V. P., Snurr, R. Q., Philp, D., Sue, A. C. H., ... Stoddart, J. F. (2020). Single-Crystal Polycationic Polymers Obtained by Single-Crystal-to-Single-Crystal Photopolymerization. Journal of the American Chemical Society, 142(13), 6180-6187. https://doi.org/10.1021/jacs.9b13790