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Molecular Weight-Dependent Oxidation and Optoelectronic Properties of Defect-Free Macrocyclic Poly(3-hexylthiophene)
| Title: | Molecular Weight-Dependent Oxidation and Optoelectronic Properties of Defect-Free Macrocyclic Poly(3-hexylthiophene) |
| Authors: | Sato, Ryohei Browse this author | | Utagawa, Atsuo Browse this author | | Fushimi, Koji Browse this author →KAKEN DB | | Li, Feng Browse this author | | Isono, Takuya Browse this author | | Tajima, Kenji Browse this author →KAKEN DB | | Satoh, Toshifumi Browse this author →KAKEN DB | | Sato, Shin-ichiro Browse this author →KAKEN DB | | Hirata, Hiroshi Browse this author →KAKEN DB | | Kikkawa, Yoshihiro Browse this author | | Yamamoto, Takuya Browse this author →KAKEN DB |
| Keywords: | cyclic polymer | | poly(3-hexylthiophene) | | molecular weight dependence | | oxidation | | polaron | | biradical | | dication | | cyclic voltammetry | | UV-Vis-NIR spectroscopy | | ESR spectroscopy |
| Issue Date: | 28-Jan-2023 |
| Publisher: | MDPI |
| Journal Title: | Polymers |
| Volume: | 15 |
| Issue: | 3 |
| Start Page: | 666 |
| Publisher DOI: | 10.3390/polym15030666 |
| Abstract: | The redox behaviors of macrocyclic molecules with an entirely pi-conjugated system are of interest due to their unique optical, electronic, and magnetic properties. In this study, defect-free cyclic P3HT with a degree of polymerization (DPn) from 14 to 43 was synthesized based on our previously established method, and its unique redox behaviors arising from the cyclic topology were investigated. Cyclic voltammetry (CV) showed that the HOMO level of cyclic P3HT decreases from -4.86 eV (14 mer) to -4.89 eV (43 mer), in contrast to the linear counterparts increasing from -4.94 eV (14 mer) to -4.91 eV (43 mer). During the CV measurement, linear P3HT suffered from electro-oxidation at the chain ends, while cyclic P3HT was stable. ESR and UV-Vis-NIR spectroscopy suggested that cyclic P3HT has stronger dicationic properties due to the interactions between the polarons. On the other hand, linear P3HT showed characteristics of polaron pairs with multiple isolated polarons. Moreover, the dicationic properties of cyclic P3HT were more pronounced for the smaller macrocycles. |
| Type: | article |
| URI: | http://hdl.handle.net/2115/88580 |
| Appears in Collections: | 工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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