Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 142, Issue 13, Pages 6180-6187Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.9b13790
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Funding
- Northwestern University
- Army Research Office [W911NF-17-1-0460]
- U.S. Department of Energy, National Nuclear Security Administration [DE-NA0003763]
- U.S. Department of Energy Office of Science (Basic Energy Sciences)
- National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility [DE-AC02-05CH11231]
- U.S. Department of Energy [DE-FG02-08ER15967]
- National Natural Science Foundation of China [21971211]
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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 angstrom). 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 (similar to 3 x 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.
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