Enhancing Polymer Photovoltaic Performance via Optimized Intramolecular Ester-Based Noncovalent Sulfur···Oxygen Interactions

Jianhua Chen, Qiaogan Liao, Gang Wang, Zhenglong Yan, Hang Wang, Yulun Wang, Xianhe Zhang, Yumin Tang, Antonio Facchetti, Tobin J Marks, Xugang Guo

Research output: Contribution to journalArticle

18 Citations (Scopus)


Head-to-head (HH) bithiophenes are typically avoided in polymer semiconductors since they engender undesirable steric repulsions, leading to a twisted backbone. While introducing electron-donating alkoxy chains can lead to intramolecular noncovalent S···O interactions, this comes at the cost of elevating the HOMOs and compromising polymer solar cell (PSC) performance. To address the limitation, a novel HH bithiophene featuring an electron-withdrawing ester functionality, 3-alkoxycarbonyl-3′-alkoxy-2,2′-bithiophene (TETOR), is synthesized. Single crystal diffraction reveals a planar TETOR conformation (versus highly twisted diester bithiophene), showing distinctive advantages of incorporating alkoxy on promoting backbone planarity. Compared to first-generation 3-alkyl-3′-alkoxy-2,2′-bithiophene (TRTOR), TETOR contains an additional planarizing (thienyl)S···O(carbonyl) interaction. Consequently, TETOR-based polymer (TffBT-TETOR) has greatly lower-lying FMOs, stronger aggregation, closer π-stacking, and better miscibility with fullerenes versus the TRTOR-based counterpart (TffBT-TRTOR). These characteristics are attributed to the additional S···O interaction and electron-withdrawing ester substituent, which enhances backbone planarity, charge transport, and PSC performance. Thus, TffBT-TETOR-based PSCs exhibit an increased PCE of 10.08%, a larger Voc of 0.76 V, and a higher Jsc of 18.30 mA cm-2 than the TffBT-TRTOR-based PSCs. These results demonstrate that optimizing intramolecular noncovalent S···O interactions by incorporating electron-withdrawing ester groups is a powerful strategy for materials invention in organic electronics.

Original languageEnglish
Pages (from-to)3874-3885
Number of pages12
Issue number10
Publication statusPublished - May 22 2018


ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Chen, J., Liao, Q., Wang, G., Yan, Z., Wang, H., Wang, Y., Zhang, X., Tang, Y., Facchetti, A., Marks, T. J., & Guo, X. (2018). Enhancing Polymer Photovoltaic Performance via Optimized Intramolecular Ester-Based Noncovalent Sulfur···Oxygen Interactions. Macromolecules, 51(10), 3874-3885. https://doi.org/10.1021/acs.macromol.8b00161