Materials Design via Optimized Intramolecular Noncovalent Interactions for High-Performance Organic Semiconductors

Xiaojie Guo, Qiaogan Liao, Eric F. Manley, Zishan Wu, Yulun Wang, Weida Wang, Tingbin Yang, Young Eun Shin, Xing Cheng, Yongye Liang, Lin X. Chen, Kang Jun Baeg, Tobin J Marks, Xugang Guo

Research output: Contribution to journalArticle

50 Citations (Scopus)

Abstract

We report the design, synthesis, and implemention in semiconducting polymers of a novel head-to-head linkage containing the TRTOR (3-alkyl-3′-alkoxy-2,2′-bithiophene) donor subunit having a single strategically optimized, planarizing noncovalent S⋯O interaction. Diverse complementary thermal, optical, electrochemical, X-ray scattering, electrical, photovoltaic, and electron microscopic characterization techniques are applied to establish structure-property correlations in a TRTOR-based polymer series. In comparison to monomers having double S⋯O interactions, replacing one alkoxy substituent with a less electron-donating alkyl one yields TRTOR-based polymers with significantly depressed (0.2-0.3 eV) HOMOs. Furthermore, the weaker single S⋯O interaction and greater TRTOR steric encumberance enhances materials processability without sacrificing backbone planarity. From another perspective, TRTOR has comparable electronic properties to ring-fused 5H-dithieno[3,2-b:2′,3′-d]pyran (DTP) subunits, but a centrosymmetric geometry which promotes a more compact and ordered structure than bulkier, axisymmetric DTP. Compared to monosubstituted TTOR (3-alkoxy-2,2′-bithiophene), alkylation at the TRTOR bithiophene 3-position enhances conjugation and polymer crystallinity with contracted π-π stacking. Grazing incidence wide-angle X-ray scattering (GIWAXS) data reveal that the greater steric hindrance and the weaker single S⋯O interaction are not detrimental to close packing and high crystallinity. As a proof of materials design, copolymerizing TRTOR with phthalimides yields copolymers with promising thin-film transistor mobility as high as 0.42 cm2/(V·s) and 6.3% power conversion efficiency in polymer solar cells, the highest of any phthalimide copolymers reported to date. The depressed TRTOR HOMOs imbue these polymers with substantially increased Ion/Ioff ratios and Voc's versus analogous subunits with multiple electron donating, planarizing alkoxy substituents. Implementing a head-to-head linkage with an alkyl/alkoxy substitution pattern and a single S⋯O interaction is a promising strategy for organic electronics materials design.

Original languageEnglish
Pages (from-to)2449-2460
Number of pages12
JournalChemistry of Materials
Volume28
Issue number7
DOIs
Publication statusPublished - Apr 26 2016

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Semiconducting organic compounds
Beam plasma interactions
Polymers
X ray scattering
Electrons
Copolymers
Phthalimides
Semiconducting polymers
Alkylation
Pyrans
Thin film transistors
Electronic properties
Conversion efficiency
Substitution reactions
Electronic equipment
Monomers
Geometry
alkoxyl radical
Ions

ASJC Scopus subject areas

  • Materials Chemistry
  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Materials Design via Optimized Intramolecular Noncovalent Interactions for High-Performance Organic Semiconductors. / Guo, Xiaojie; Liao, Qiaogan; Manley, Eric F.; Wu, Zishan; Wang, Yulun; Wang, Weida; Yang, Tingbin; Shin, Young Eun; Cheng, Xing; Liang, Yongye; Chen, Lin X.; Baeg, Kang Jun; Marks, Tobin J; Guo, Xugang.

In: Chemistry of Materials, Vol. 28, No. 7, 26.04.2016, p. 2449-2460.

Research output: Contribution to journalArticle

Guo, X, Liao, Q, Manley, EF, Wu, Z, Wang, Y, Wang, W, Yang, T, Shin, YE, Cheng, X, Liang, Y, Chen, LX, Baeg, KJ, Marks, TJ & Guo, X 2016, 'Materials Design via Optimized Intramolecular Noncovalent Interactions for High-Performance Organic Semiconductors', Chemistry of Materials, vol. 28, no. 7, pp. 2449-2460. https://doi.org/10.1021/acs.chemmater.6b00850
Guo, Xiaojie ; Liao, Qiaogan ; Manley, Eric F. ; Wu, Zishan ; Wang, Yulun ; Wang, Weida ; Yang, Tingbin ; Shin, Young Eun ; Cheng, Xing ; Liang, Yongye ; Chen, Lin X. ; Baeg, Kang Jun ; Marks, Tobin J ; Guo, Xugang. / Materials Design via Optimized Intramolecular Noncovalent Interactions for High-Performance Organic Semiconductors. In: Chemistry of Materials. 2016 ; Vol. 28, No. 7. pp. 2449-2460.
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N2 - We report the design, synthesis, and implemention in semiconducting polymers of a novel head-to-head linkage containing the TRTOR (3-alkyl-3′-alkoxy-2,2′-bithiophene) donor subunit having a single strategically optimized, planarizing noncovalent S⋯O interaction. Diverse complementary thermal, optical, electrochemical, X-ray scattering, electrical, photovoltaic, and electron microscopic characterization techniques are applied to establish structure-property correlations in a TRTOR-based polymer series. In comparison to monomers having double S⋯O interactions, replacing one alkoxy substituent with a less electron-donating alkyl one yields TRTOR-based polymers with significantly depressed (0.2-0.3 eV) HOMOs. Furthermore, the weaker single S⋯O interaction and greater TRTOR steric encumberance enhances materials processability without sacrificing backbone planarity. From another perspective, TRTOR has comparable electronic properties to ring-fused 5H-dithieno[3,2-b:2′,3′-d]pyran (DTP) subunits, but a centrosymmetric geometry which promotes a more compact and ordered structure than bulkier, axisymmetric DTP. Compared to monosubstituted TTOR (3-alkoxy-2,2′-bithiophene), alkylation at the TRTOR bithiophene 3-position enhances conjugation and polymer crystallinity with contracted π-π stacking. Grazing incidence wide-angle X-ray scattering (GIWAXS) data reveal that the greater steric hindrance and the weaker single S⋯O interaction are not detrimental to close packing and high crystallinity. As a proof of materials design, copolymerizing TRTOR with phthalimides yields copolymers with promising thin-film transistor mobility as high as 0.42 cm2/(V·s) and 6.3% power conversion efficiency in polymer solar cells, the highest of any phthalimide copolymers reported to date. The depressed TRTOR HOMOs imbue these polymers with substantially increased Ion/Ioff ratios and Voc's versus analogous subunits with multiple electron donating, planarizing alkoxy substituents. Implementing a head-to-head linkage with an alkyl/alkoxy substitution pattern and a single S⋯O interaction is a promising strategy for organic electronics materials design.

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