Augmented Self-Association by Electrostatic Forces in Thienopyrrole-Fused Thiadiazoles that Contain an Ester instead of an Ether Linker

Yukako Naito, Ryo Moriguchi, Chitoshi Kitamura, Taisuke Matsumoto, Toshitada Yoshihara, Tsutomu Ishi-i, Yuka Nagata, Hiroki Takeshita, Kazunari Yoshizawa, Yoshihito Shiota, Kazumasa Suzuki, Shin ichiro Kato

Research output: Contribution to journalArticlepeer-review

Abstract

During the self-assembly of π-conjugated molecules, linkers and substituents can potentially add supportive noncovalent intermolecular interactions to π-stacking interactions. Here, we report the self-assembly behavior of thienopyrrole-fused thiadiazole (TPT) fluorescent dyes that possess ester or ether linkers and dodecyloxy side chains in solution and the condensed phase. A comparison of the self-association behavior of the ester- and ether-bridged compounds in solution using detailed UV-vis, fluorescence, and NMR spectroscopic studies revealed that the subtle replacement of the ether linkers by ester linkers leads to a distinct increase in the association constant (ca. 3–4 fold) and the enthalpic contribution (ca. 3 kcal mol−1). Theoretical calculations suggest that the ester linkers, which are in close proximity to one another due to the π-stacking interactions, induce attractive electrostatic forces and augment self-association. The self-assembly of TPT dyes into well-defined 1D clusters with high aspect ratios was observed, and their morphologies and crystallinity were investigated using SEM and X-ray diffraction analyses. TPTs with ester linkers exhibit a columnar liquid crystalline mesophase in the condensed phase.

Original languageEnglish
Article numbere202101341
JournalChemistry - An Asian Journal
Volume17
Issue number4
DOIs
Publication statusPublished - Feb 14 2022

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Organic Chemistry

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