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

TitleSingle-Crystal Polycationic Polymers Obtained by Single-Crystal-to-Single-Crystal Photopolymerization
Authors
Issue Date2020
Citation
Journal of the American Chemical Society, 2020, v. 142, n. 13, p. 6180-6187 How to Cite?
AbstractThe 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.
Persistent Identifierhttp://hdl.handle.net/10722/333421
ISSN
2023 Impact Factor: 14.4
2023 SCImago Journal Rankings: 5.489
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorGuo, Qing Hui-
dc.contributor.authorJia, Manping-
dc.contributor.authorLiu, Zhichang-
dc.contributor.authorQiu, Yunyan-
dc.contributor.authorChen, Hongliang-
dc.contributor.authorShen, Dengke-
dc.contributor.authorZhang, Xuan-
dc.contributor.authorTu, Qing-
dc.contributor.authorRyder, Matthew R.-
dc.contributor.authorChen, Haoyuan-
dc.contributor.authorLi, Peng-
dc.contributor.authorXu, Yaobin-
dc.contributor.authorLi, Penghao-
dc.contributor.authorChen, Zhijie-
dc.contributor.authorShekhawat, Gajendra S.-
dc.contributor.authorDravid, Vinayak P.-
dc.contributor.authorSnurr, Randall Q.-
dc.contributor.authorPhilp, Douglas-
dc.contributor.authorSue, Andrew C.H.-
dc.contributor.authorFarha, Omar K.-
dc.contributor.authorRolandi, Marco-
dc.contributor.authorStoddart, J. Fraser-
dc.date.accessioned2023-10-06T05:19:15Z-
dc.date.available2023-10-06T05:19:15Z-
dc.date.issued2020-
dc.identifier.citationJournal of the American Chemical Society, 2020, v. 142, n. 13, p. 6180-6187-
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10722/333421-
dc.description.abstractThe 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.-
dc.languageeng-
dc.relation.ispartofJournal of the American Chemical Society-
dc.titleSingle-Crystal Polycationic Polymers Obtained by Single-Crystal-to-Single-Crystal Photopolymerization-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/jacs.9b13790-
dc.identifier.pmid32017550-
dc.identifier.scopuseid_2-s2.0-85080071773-
dc.identifier.volume142-
dc.identifier.issue13-
dc.identifier.spage6180-
dc.identifier.epage6187-
dc.identifier.eissn1520-5126-
dc.identifier.isiWOS:000526393700036-

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