Molecular Weight-Dependent Oxidation and Optoelectronic Properties of Defect-Free Macrocyclic Poly(3-hexylthiophene)
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Nuclear Magnetic Resonance (NMR) Spectroscopy
2.3. Analytical Size Exclusion Chromatography (SEC)
2.4. Preparative SEC
2.5. Matrix-Assisted Laser Desorption Ionization Time-of-Flight (MALDI-TOF) Mass Spectrometry
2.6. UV–Vis and UV–Vis–NIR Spectroscopies
2.7. Raman Spectroscopy
2.8. Scanning Tunneling Microscope (STM)
2.9. Cyclic Voltammetry (CV)
2.10. Spectroelectrochemistry
2.11. Preparation of Radical Cation (P3HT•+) and Dication (P3HT2+)
2.12. Electron Spin Resonance (ESR) Spectroscopy
2.13. Data Fitting of ESR Spectra
3. Results and Discussion
3.1. Synthesis
3.2. SEC
3.3. STM
3.4. Raman Spectroscopy
3.5. UV–Vis Spectroscopy
3.6. CV
3.7. Spectroelectrochemistry
3.8. UV–Vis–NIR Spectroscopy of Chemically Oxidized P3HT
3.9. ESR Spectroscopy
3.10. VT 1H NMR Spectroscopy
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Mn,SEC (g·mol–1) a | Mp,SEC (g·mol–1) a | Mw/Mn | Mp,C/Mp,L | |
---|---|---|---|---|
L14 | 2300 | 2400 | 1.07 | 0.92 |
C14 | 2200 | 2200 | 1.03 | |
L21 | 3500 | 3500 | 1.05 | 0.83 |
C21 | 2900 | 2900 | 1.04 | |
L26 | 4300 | 4100 | 1.08 | 0.76 |
C26 | 3100 | 3100 | 1.05 | |
L29 | 5100 | 5300 | 1.17 | 0.68 |
C29 | 3900 | 3600 | 1.08 | |
L43 | 7200 | 8700 | 1.13 | 0.71 |
C43 | 5700 | 6200 | 1.19 |
Abs λmax (nm) a | Abs λonset (nm) a,b | (eV) b | (V) c | HOMO (eV) d | |
---|---|---|---|---|---|
L14 | 438 | 527 | 2.35 | 0.14 | –4.94 |
C14 | 426 | 527 | 2.35 | 0.06 | –4.86 |
L21 | 444 | 531 | 2.33 | 0.12 | –4.92 |
C21 | 433 | 528 | 2.35 | 0.09 | –4.89 |
L26 | 446 | 534 | 2.32 | 0.10 | –4.90 |
C26 | 438 | 530 | 2.34 | 0.10 | –4.90 |
L29 | 448 | 534 | 2.32 | 0.10 | –4.90 |
C29 | 441 | 533 | 2.33 | 0.11 | –4.91 |
L43 | 452 | 537 | 2.31 | 0.07 | –4.91 |
C43 | 448 | 538 | 2.30 | 0.12 | –4.89 |
Transition (nm) | ||||
---|---|---|---|---|
TN a | TC b | TP/B + C c | TP/B d | |
L14 | 442 | - | 815 | >2200 |
C14 | 428 | - | 742 | 1440 |
L21 | 447 | 562 | 766 | >2200 |
C21 | 437 | about 500 | 755 | about 1700 |
L29 | 450 | 551 | 797 | >2200 |
C29 | 442 | 508 | 773 | 1850 |
L43 | 453 | 566 | - | - |
C43 | 449 | 532 | 782 | >2200 |
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Sato, R.; Utagawa, A.; Fushimi, K.; Li, F.; Isono, T.; Tajima, K.; Satoh, T.; Sato, S.-i.; Hirata, H.; Kikkawa, Y.; et al. Molecular Weight-Dependent Oxidation and Optoelectronic Properties of Defect-Free Macrocyclic Poly(3-hexylthiophene). Polymers 2023, 15, 666. https://doi.org/10.3390/polym15030666
Sato R, Utagawa A, Fushimi K, Li F, Isono T, Tajima K, Satoh T, Sato S-i, Hirata H, Kikkawa Y, et al. Molecular Weight-Dependent Oxidation and Optoelectronic Properties of Defect-Free Macrocyclic Poly(3-hexylthiophene). Polymers. 2023; 15(3):666. https://doi.org/10.3390/polym15030666
Chicago/Turabian StyleSato, Ryohei, Atsuo Utagawa, Koji Fushimi, Feng Li, Takuya Isono, Kenji Tajima, Toshifumi Satoh, Shin-ichiro Sato, Hiroshi Hirata, Yoshihiro Kikkawa, and et al. 2023. "Molecular Weight-Dependent Oxidation and Optoelectronic Properties of Defect-Free Macrocyclic Poly(3-hexylthiophene)" Polymers 15, no. 3: 666. https://doi.org/10.3390/polym15030666