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Title: Helical Poly(5-alkyl-2,3-thiophene)s: Controlled Synthesis and Structure Characterization

Journal Article · · Macromolecules
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Whereas Poly(3-alkyl-2,5-thiophene)s (P3AT), with many potential applications, have been extensively investigated, their ortho-connected isomers, poly(5-alkyl-2,3-thiophene)s (P5AT), have never been reported because of the difficulty in their syntheses. We herein present the first synthesis of regioregular P5AT via controlled Suzuki cross-coupling polymerization with PEPPSI-IPr as catalyst, affording the polymers with tunable molecular weight, narrow polydispersity (PDI) and well-defined functional end groups at the gram scale. The helical geometry of P5AT was studied by a combination of NMR, small angle x-ray scattering (SAXS) and scanning tunneling microscopy (STM). Particularly, the single polymer chain of poly(5- 2 butyl-2,3-thiophene) (P5BT) on highly oriented pyrolytic graphite (HOPG) substrates with either M or P helical conformation was directly observed by STM. The comparison of UV-vis absorption between poly(5-hexyl-2,3-thiophene) (P5HT) (λ = 345 nm) and poly(3-hexyl-2,5- thiophene) (P3HT) (λ = 450 nm) indicated that the degree of conjugation of the backbone in P5HT is less than in P3HT, which may be a consequence of the helical geometry of the former compared to the more planar geometry of the latter. Moreover, we found that P5HT can emit green fluorescence under UV (λ = 360 nm) irradiation

Research Organization:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1265664
Journal Information:
Macromolecules, Vol. 49, Issue 13; ISSN 0024-9297
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 20 works
Citation information provided by
Web of Science

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Cited By (6)

Intramolecular Catalyst Transfer over Sterically Hindered Arenes in Suzuki Cross‐Coupling Reactions journal July 2019
Twist sense control in terminally functionalized ortho -phenylenes journal January 2018
Controlled synthesis of ortho , para -alternating linked polyarenes via catalyst-transfer Suzuki coupling polymerization journal January 2018
Synthesis of a one-handed helical polythiophene: a new approach using an axially chiral bithiophene with a fixed syn -conformation journal January 2019
Recent developments in the synthesis of regioregular thiophene-based conjugated polymers for electronic and optoelectronic applications using nickel and palladium-based catalytic systems journal January 2020
Diversifying Cross-Coupling Strategies, Catalysts and Monomers for the Controlled Synthesis of Conjugated Polymers journal June 2018

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