Chain-Length-Dependent Self-Assembly Behaviors of Discrete Conjugated Oligo(3-hexylthiophene)
- Authors
- Kim, Youngkwon; Park, Hyeonjung; Abdilla, Allison; Yun, Hongseok; Han, Junghun; Stein, Gila E.; Hawker, Craig J.; Kim, Bumjoon J.
- Issue Date
- Apr-2020
- Publisher
- AMER CHEMICAL SOC
- Citation
- CHEMISTRY OF MATERIALS, v.32, no.8, pp.3597 - 3607
- Indexed
- SCIE
SCOPUS
- Journal Title
- CHEMISTRY OF MATERIALS
- Volume
- 32
- Number
- 8
- Start Page
- 3597
- End Page
- 3607
- URI
- https://scholarworks.bwise.kr/hanyang/handle/2021.sw.hanyang/145833
- DOI
- 10.1021/acs.chemmater.0c00869
- ISSN
- 0897-4756
- Abstract
- Discrete oligomers (i.e., highly monodisperse) can provide a deep understanding of chain-length-dependent properties of polymers and their self-assembly behaviors. Herein, discrete oligo(3-hexylthiophene)s (D-o3HTs) with a dispersity (D) of 1.0 and degree of polymerization (DP) between 6 and 18 were obtained through a simple synthetic procedure of 3-hexlythiophene trimer-based polymerizations and automated column chromatography purification. As the DP of D-o3HTs increases, longer conjugation lengths cause red shifts in their optical properties and yield tunable crystalline properties. Interestingly, D-o3HTs with DP <= 9 have a dominant face-on Form II structure in thin films, while a fiber morphology is also not observed in thin films. In contrast, D-o3HTs with DP >= 12 assemble into a dominant edge-on Form I structure in thin films and show highly ordered fiber morphologies. In addition, Bragg rod patterns are observed in thin films by transmission electron microscopy and grazing incidence X-ray scattering with these patterns being distinctive when compared to those for conventional regioregular poly(3-hexylthiophene) with D = 1.1. Finally, the formation of 2-dimensional flowerlike nanostructures with overall micrometer dimensions is obtained from D-o3HTs via solvent-mediated self-assembly. These results offer an understanding of self-assembly behaviors of discrete conjugated polymers, leading to exquisite control over their crystallinity and nanoscale morphology.
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