Journal
CHEMISTRY OF MATERIALS
Volume 30, Issue 4, Pages 1417-1426Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.chemmater.7b05303
Keywords
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Funding
- NSF Polymers Program [DMR 1608297]
- AFOSR MURI program [FA9550-12-1]
- National Institute of Standards and Technology [DMR-1508249]
- National Science Foundation [DMR-1508249]
- National Institute of Standards and Technology, U.S. Department of Commerce
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-76SF00515]
- Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy [DE-AC02-05CH11231]
- MRSEC Program of the NSF [DMR 1720256]
- Direct For Mathematical & Physical Scien
- Division Of Materials Research [1608297] Funding Source: National Science Foundation
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A conjugated polyelectrolyte (poly[2,6-(4,4-bis-potassium butanylsulfonate-4H-cydopenta-[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)], PCPDTBT-SO3K) assembles into a novel, hierarchical hydrogel structure with all structural evidence indicating dominant electrostatic rather than aromatic or mesogen interactions. PCPDTBT-SO3K forms an entangled polymer mesh, where polymer chains are tied together by ionic cross-links, comprising microgel clusters that percolate to form a macroscopic three-dimensional network. With increasing temperature, ions gain mobility to move toward the exterior of the microgel clusters, dissolving the ionic cross-links and inhibiting network percolation through electrostatic repulsion. While pi-pi stacking interactions may be present in a disorganized fashion, no long-range pi-pi stacking is evident in X-ray scattering. Soft materials based on PCPDTBT-SO3K remain semiconducting and exhibit elevated ionic conductivity at the structural reorganization temperature.
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