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. 2022 Jul 6;12(30):19548-19553.
doi: 10.1039/d2ra02669d. eCollection 2022 Jun 29.

Fullerene C70/porphyrin hybrid nanoarchitectures: single-cocrystal nanoribbons with ambipolar charge transport properties

Takatsugu Wakahara  1 , Kahori Nagaoka  1 , Chika Hirata  1 , Kun'ichi Miyazawa  2 , Kazuko Fujii  1 , Yoshitaka Matsushita  3 , Osamu Ito  1 , Makito Takagi  4 , Tomomi Shimazaki  4 , Masanori Tachikawa  4 , Yoshiki Wada  1 , Shinjiro Yagyu  1 , Yubin Liu  5 , Yoshiyuki Nakajima  5 , Kazuhito Tsukagoshi  6
Affiliations

Fullerene C70/porphyrin hybrid nanoarchitectures: single-cocrystal nanoribbons with ambipolar charge transport properties

Takatsugu Wakahara et al. RSC Adv. .

Abstract

In recent years, supramolecular cocrystals containing organic donors and acceptors have been explored as active components in organic field-effect transistors (FETs). Herein, we report the synthesis of novel single-cocrystal nanoribbons with ambipolar charge transport characteristics from C70 and 5,10,15,20-tetrakis(3,5-dimethoxyphenyl)porphyrin (3,5-TPP) in a 3 : 2 ratio. The C70/3,5-TPP nanoribbons exhibited a new strong absorption band in the near-infrared region, indicating the presence of charge-transfer interactions between C70 and 3,5-TPP in the cocrystals. We elucidated the mechanism of the charge-transport properties of the nanoribbons using photoemission yield spectroscopy in air and theoretical calculations. A strong interaction between porphyrins in the one-dimensional porphyrin chains formed in C70/3,5-TPP nanoribbons, which was confirmed by single-crystal X-ray diffraction, plays a crucial role in their hole transport properties.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. (a) Optical microscopy image and (b) SEM image of C70/3,5-TPP nanoribbons.
Fig. 2
Fig. 2. Diffuse reflectance spectra in Vis and near-infrared regions (K/M: Kubelka–Munk function, which is proportional to absorbance); (a) C70/3,5-TPP nanoribbons, (b) C70 crystals, (c) 3,5-TPP film, (d) subtraction of normalized absorption spectra at 610 nm as shown in (a) and (b).
Fig. 3
Fig. 3. Steady-state fluorescence spectra of 3,5-TPP crystals (black) and C70/3,5-TPP nanoribbons (red); λex: 520 nm. Inset: Time profiles of fluorescence intensity [λex: 520 nm, λem: 690–730 nm for 3,5-TPP crystals (black) and λem: 780–820 nm for C70/3,5-TPP nanoribbons (red)].
Fig. 4
Fig. 4. Transfer (ID–VG) characteristics of C70/3,5-TPP nanoribbons recorded in dark conditions. The solid curve displays drain current (ID) as a function of gate voltage (VG), and the dotted curve shows the square root of ID (right vertical axis).
Fig. 5
Fig. 5. (a) PYSA spectra and (b) energy level diagrams of C60/3,5-TPP cocrystals, 3,5-TPP, C70/3,5-TPP nanoribbons, and C70 powder. For semi-conductor, the HOMO and the LUMO correspond to the top of the valence band and bottom of the conduction band, respectively.
Fig. 6
Fig. 6. Crystal structure of a C70/3,5-TPP nanoribbons, (a) [(3,5-TPP)2·(C70)3·(toluene)3] unit structure (b) [(3,5-TPP)2·(C70)3·(toluene)3]2 unit structure (c) the [C70/(3,5-TPP)/C70]2 unit structure, and (d) one-dimensional porphyrin chains unit structure. Red arrows indicate the toluene molecules in the crystals.
Fig. 7
Fig. 7. TPPs structures extracted (a) C60/3,5-TPP and (b) C70/3,5-TPP cocrystals. The distance between porphyrins in C70/3,5-TPP is shorter than that in C60/3,5-TPP. The molecular orbital of (c) HOMO and (d) HOMO-3, which are localized at the center and side chains of TPP, respectively. The interaction between side chains of 3,5-TPPs gives a larger coupling constant.
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References

    1. Kim F. S. Ren G. Jenekhe S. A. Chem. Mater. 2011;23:682–732. doi: 10.1021/cm102772x. - DOI
    1. Zang L. Che Y. Moore J. S. Acc. Chem. Res. 2008;41:1596–1608. doi: 10.1021/ar800030w. - DOI - PubMed
    1. Zhao Y. S. Fu H. Peng A. Ma Y. Liao Q. Yao J. Acc. Chem. Res. 2010;43:409–418. doi: 10.1021/ar900219n. - DOI - PubMed
    1. Zaumseil J. Sirringhaus H. Chem. Rev. 2007;107:1296–1323. doi: 10.1021/cr0501543. - DOI - PubMed
    1. Li H. Tee B. C. K. Cha J. J. Cui Y. Chung J. W. Lee S. Y. Bao Z. J. Am. Chem. Soc. 2012;134:2760–2765. doi: 10.1021/ja210430b. - DOI - PubMed