Abstract
Although organic semiconductors with high mobility and thermal stability are particularly desirable for practical applications, facile methods for their development still remains a big challenge. In this work, a charge-transfer cocrystal based on fullerene (C70)/cobalt porphyrin supramolecular architecture was prepared by a solution-processable co-assembly strategy. This supramolecular architecture showed hole mobility as high as 4.21 cm2·V−1·s−1, and a relatively high mobility of 0.02 cm2·V−1·s−1 even after thermal treatment at 1,000 °C. Further studies confirmed the occurrence of charge-transfer from 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrinato cobalt(II) (CoTMPP) to C70 and the paramagnetic character within the supramolecular system. These factors were found to be responsible for the aforementioned superior performances. Thus, a novel organic semiconductor has been reported in this work, which can be potentially used for next generation electronic devices. Furthermore, it has been demonstrated that charge-transfer co-crystallization is a powerful strategy for the rational design and construction of a broad class of new multifunctional organic co-crystalline materials.
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Giri, G.; Verploegen, E.; Mannsfeld, S. C. B.; Atahan-Evrenk, S.; Kim, D. H.; Lee, S. Y.; Becerril, H. A.; Aspuru-Guzik, A.; Toney, M. F.; Bao, Z. Tuning charge transport in solution-sheared organic semiconductors using lattice strain. Nature 2011, 480, 504–508.
Chen, Y. S.; Xu, Y. F.; Zhao, K.; Wan, X. J.; Deng, J. C.; Yan, W. B. Towards flexible all-carbon electronics: Flexible organic field-effect transistors and inverter circuits using solution-processed all-graphene source/drain/gate electrodes. Nano Res. 2010, 3, 714–721.
Lei, Y. L.; Jin, Y.; Zhou, D. Y.; Gu, W.; Shi, X. B.; Liao, L. S.; Lee, S. T. White-light emitting microtubes of mixed organic charge-transfer complexes. Adv. Mater. 2012, 24, 5345–5351.
Kim, F. S.; Guo, X. G.; Watson, M. D.; Jenekhe, S. A. High-mobility ambipolar transistors and high-gain inverters from a donor-acceptor copolymer semiconductor. Adv. Mater. 2010, 22, 478–482.
Li, Y. J.; Liu, T. F.; Liu, H. B.; Tian, M.-Z.; Li, Y. L. Self-assembly of intramolecular charge-transfer compounds into functional molecular systems. Acc. Chem. Res. 2014, 47, 1186–1198.
Zhu, W. G.; Zheng, R. H.; Fu, X. L.; Fu, H. B.; Shi, Q.; Zhen, Y. G.; Dong, H. L.; Hu, W. P. Revealing the chargetransfer interactions in self-assembled organic cocrystals: Two-dimensional photonic applications. Angew. Chem., Int. Ed. 2015, 54, 6785–6789.
Busseron, E.; Cid, J.-J.; Wolf, A.; Du, G. Y.; Moulin, E.; Fuks, G.; Maaloum, M.; Polavarapu, P.; Ruff, A.; Saur, A.-K. et al. Light-controlled morphologies of self-assembled triarylamine–fullerene conjugates. ACS Nano 2015, 9, 2760–2772.
Wuest, J. D. Molecular solids: Co-crystals give light a tune-up. Nat. Chem. 2012, 4, 74–75.
Jérome, D. Organic conductors: From charge density wave TTF−TCNQ to superconducting (TMTSF)2PF6. Chem. Rev. 2004, 104, 5565–5592.
Qin, W.; Chen, X. M.; Lohrman, J.; Gong, M. G.; Yuan, G. L.; Wuttig, M.; Ren, S. Q. External stimuli controlled multiferroic charge-transfer crystals. Nano Res. 2016, 9, 925–932.
Yang, J.; Heo, M.; Lee, H. J.; Park, S.-M.; Kim, J. Y.; Shin, H. S. Reduced graphene oxide (rGO)-wrapped fullerene (C60) wires. ACS Nano 2011, 5, 8365–8371.
Qin, W.; Chen, X. M.; Li, H. S.; Gong, M. G.; Yuan, G. L.; Grossman, J. C.; Wuttig, M.; Ren, S. Q. Room temperature multiferroicity of charge transfer crystals. ACS Nano 2015, 9, 9373–9379.
Zhang, J.; Tan, J. H.; Ma, Z. Y.; Xu, W.; Zhao, G. Y.; Geng, H.; Di, C. A.; Hu, W. P.; Shuai, Z. G.; Singh, K. et al. Fullerene/sulfur-bridged annulene cocrystals: Two-dimensional segregated heterojunctions with ambipolar transport properties and photoresponsivity. J. Am. Chem. Soc. 2013, 135, 558–561.
Wakahara, T.; D’Angelo, P.; Miyazawa, K. I.; Nemoto, Y.; Ito, O.; Tanigaki, N.; Bradley, D. D. C.; Anthopoulos, T. D. Fullerene/cobalt porphyrin hybrid nanosheets with ambipolar charge transporting characteristics. J. Am. Chem. Soc. 2012, 134, 7204–7206.
Armaroli, N.; Marconi, G.; Echegoyen, L.; Bourgeois, J.-P.; Diederich, F. Charge-transfer interactions in face-to-face porphyrin-fullerene systems: Solvent-dependent luminescence in the infrared spectral region. Chem.—Eur. J. 2000, 6, 1629–1645.
Guldi, D. M. Fullerene-porphyrin architectures; photosynthetic antenna and reaction center models. Chem. Soc. Rev. 2002, 31, 22–36.
Yokota, T.; Kuribara, K.; Tokuhara, T.; Zschieschang, U.; Klauk, H.; Takimiya, K.; Sadamitsu, Y.; Hamada, M.; Sekitani, T.; Someya, T. Flexible low-voltage organic transistors with high thermal stability at 250 °C. Adv. Mater. 2013, 25, 3639–3644.
Ling, Q.-D.; Kang, E.-T.; Neoh, K.-G.; Chen, Y.; Zhuang, X.-D.; Zhu, C. X.; Chan, D. S. H. Thermally stable polymer memory devices based on a π-conjugated triad. Appl. Phys. Lett. 2008, 92, 143302.
Qi, Z.; Cao, J. M.; Li, H.; Ding, L. M.; Wang, J. Z. High-performance thermally stable organic phototransistors based on PSeTPTI/PC61BM for visible and ultraviolet photodetection. Adv. Funct. Mater. 2015, 25, 3138–3146.
Saito, M.; Yamamoto, T.; Osaka, I.; Miyazaki, E.; Takimiya, K.; Kuwabara, H.; Ikeda, M. ChemInform abstract: Facile synthesis of [1]benzothieno[3,2-b]benzothiophene from o-dihalostilbenes. ChemInform 2011, 42, DOI: 10.1002/chin.201101086.
Kuribara, K.; Wang, H.; Uchiyama, N.; Fukuda, K.; Yokota, T.; Zschieschang, U.; Jaye, C.; Fischer, D.; Klauk, H.; Yamamoto, T. et al. Organic transistors with high thermal stability for medical applications. Nat. Commun. 2012, 3, 723.
Salim, T.; Lee, H.-W.; Wong, L. H.; Oh, J. H.; Bao, Z. A.; Lam, Y. M. Semiconducting carbon nanotubes for improved efficiency and thermal stability of polymer–fullerene solar cells. Adv. Funct. Mater. 2016, 26, 51–65.
Abe, M.; Mori, T.; Osaka, I.; Sugimoto, K.; Takimiya, K. Thermally, operationally, and environmentally stable organic thin-film transistors based on bis[1]benzothieno[2,3-d:2′,3′ -d′]naphtho[2,3-b:6,7-b′]dithiophene derivatives: Effective synthesis, electronic structures, and structure–property relationship. Chem. Mater. 2015, 27, 5049–5057.
Zheng, S. S.; Lu, X. Formation kinetics and photoelectrochemical properties of crystalline C70 one-dimensional microstructures. RSC Adv. 2015, 5, 38202–38208.
Zhao, Y.; Truhlar, D. G. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: Two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor. Chem. Acc. 2008, 120, 215–241.
Schwerdtfeger, P.; Dolg, M.; Schwarz, W. H. E.; Bowmaker, G. A.; Boyd, P. D. W. Relativistic effects in gold chemistry. I. Diatomic gold compounds. J. Chem. Phys. 1989, 91, 1762–1774.
Andrae, D.; Häußermann, U.; Dolg, M.; Stoll, H.; Preuß, H. Energy-adjusted ab initio pseudopotentials for the second and third row transition elements. Theoret. Chim. Acta 1990, 77, 123–141.
Bergner, A.; Dolg, M.; Küchle, W.; Stoll, H.; Preuß, H. Ab initio energy-adjusted pseudopotentials for elements of groups 13–17. Mol. Phys. 1993, 80, 1431–1441.
Hehre, W. J.; Ditchfield, R.; Pople, J. A. Self-consistent molecular orbital methods. XII. Further extensions of gaussian-type basis sets for use in molecular orbital studies of organic molecules. J. Chem. Phys. 1972, 56, 2257–2261.
Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.et al .Gaussian 09, Revision A.02; Gaussian, Inc.: Wallingford, CT, USA, 2016.
Miyazawa, K.; Kuwasaki, Y.; Obayashi, A.; Kuwabara, M. C60 nanowhiskers formed by the liquid–liquid interfacial precipitation method. J. Mater. Res. 2002, 17, 83–88.
Hasobe, T.; Sandanayaka, A. S. D.; Wada, T.; Araki, Y. Fullerene-encapsulated porphyrin hexagonal nanorods. An anisotropic donor-acceptor composite for efficient photoinduced electron transfer and light energy conversion. Chem. Commun. 2008, 3372–3374.
Konarev, D. V.; Kovalevsky, A. Y.; Li, X.; Neretin, I. S.; Litvinov, A. L.; Drichko, N. Y. V.; Slovokhotov, Y. L.; Coppens, P.; Lyubovskaya, R. N. Synthesis and structure of multicomponent crystals of fullerenes and metal tetraarylporphyrins. Inorg. Chem. 2002, 41, 3638–3646.
Herrmann, I.; Kramm, U. I.; Fiechter, S.; Bogdanoff, P. Oxalate supported pyrolysis of CoTMPP as electrocatalysts for the oxygen reduction reaction. Electrochim. Acta 2009, 54, 4275–4287.
Herrmann, I.; Kramm, U. I.; Fiechter, S.; Brüser, V.; Kersten, H.; Bogdanoff, P. Comparative study of the carbonisation of CoTMPP by low temperature plasma and heat treatment. Plasma Process. Polym. 2010, 7, 515–526.
Céolin, R.; Tamarit, J. L.; Barrio, M.; López, D. O.; Toscani, S.; Allouchi, H.; Agafonov, V.; Szwarc, H. Solid-state studies on a cubic 1:1 solvate of C60 grown from dichloromethane and leading to another hexagonal C60 polymorph. Chem. Mater. 2001, 13, 1349–1355.
Zheng, S. S.; Xu, M. L.; Lu, X. Facile method toward hierarchical fullerene architectures with enhanced hydrophobicity and photoluminescence. ACS Appl. Mater. Interfaces 2015, 7, 20285–20291.
Li, C. Z.; Chueh, C. C.; Yip, H. L.; Ding, F. Z.; Li, X. S.; Jen, A. K. Y. Solution-processible highly conducting fullerenes. Adv. Mater. 2013, 25, 2457–2461.
Ji, H. X.; Hu, J. S.; Wan, L. J.; Tang, Q. X.; Hu, W. P. Controllable crystalline structure of fullerene nanorods and transport properties of an individual nanorod. J. Mater. Chem. 2008, 18, 328–332.
Sato, S.; Seki, S.; Luo, G. F.; Suzuki, M.; Lu, J.; Nagase, S.; Akasaka, T. Tunable charge-transport properties of Ih- C80endohedral metallofullerenes: Investigation of La2@C80, Sc3N@C80, and Sc3C2@C80. J. Am. Chem. Soc. 2012, 134, 11681–11686.
Barnes, J. C.; Dale, E. J.; Prokofjevs, A.; Narayanan, A.; Gibbs-Hall, I. C.; Juríček, M.; Stern, C. L.; Sarjeant, A. A.; Botros, Y. Y.; Stupp, S. I. et al. Semiconducting single crystals comprising segregated arrays of complexes of C60. J. Am. Chem. Soc. 2015, 137, 2392–2399.
Guo, Y. G.; Li, C. J.; Wan, L. J.; Chen, D. M.; Wang, C. R.; Bai, C. L.; Wang, Y. G. Well-defined fullerene nanowire arrays. Adv. Funct. Mater. 2003, 13, 626–630.
Li, H. Y.; Tee, B. C. K.; Cha, J. J.; Cui, Y.; Chung, J. W.; Lee, S. Y.; Bao, Z. A. High-mobility field-effect transistors from large-area solution-grown aligned C60single crystals. J. Am. Chem. Soc.
Fajer, J.; Borg, D. C.; Forman, A.; Dolphin, D.; Felton, R. H..pi.-Cation radicals and dications of metalloporphyrins. J. Am. Chem. Soc. 1970, 92, 3451–3459.
Sato, S.; Nikawa, H.; Seki, S.; Wang, L.; Luo, G. F.; Lu, J.; Haranaka, M.; Tsuchiya, T.; Nagase, S.; Akasaka, T. A co-crystal composed of the paramagnetic endohedral metallofullerene La@C82 and a nickel porphyrin with high electron mobility. Angew. Chem., Int. Ed. 2012, 51, 1589–1591.
Boyd, P. D. W.; Reed, C. A. Fullerene−porphyrin constructs. Acc. Chem. Res. 2005, 38, 235–242.
Ren, J.; Meng, S.; Kaxiras, E. Theoretical investigation of the C60/copper phthalocyanine organic photovoltaic heterojunction. Nano Res. 2012, 5, 248–257.
Goetz, K. P.; Vermeulen, D.; Payne, M. E.; Kloc, C.; McNeil, L. E.; Jurchescu, O. D. Charge-transfer complexes: New perspectives on an old class of compounds. J. Mater. Chem. C 2014, 2, 3065–3076.
Acknowledgements
Financial support from the National Thousand Talents Program of China, the National Natural Science Foundation of China (Nos. 51472095, 51602112, 51672093 and 21103224), Program for Changjiang Scholars and Innovative Research Team in University (No. IRT1014), Key Laboratory of Functional Inorganic Material Chemistry (Heilongjiang University), and Ministry of Education are gratefully acknowledged. This work was partially supported by Japan Society for the Promotion of Science (JSPS) (Nos. JP16F16360, 26102011, 26249145, and 15K21721). We thank the Analytical and Testing Center in Huazhong University of Science and Technology for all related measurements. We also acknowledge Dr. Akihiko Fujiwara and Dr. Kunihisa Sugimoto for single-crystal XRD measurement.
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Zheng, S., Zhong, J., Matsuda, W. et al. Fullerene/cobalt porphyrin charge-transfer cocrystals: Excellent thermal stability and high mobility. Nano Res. 11, 1917–1927 (2018). https://doi.org/10.1007/s12274-017-1809-7
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DOI: https://doi.org/10.1007/s12274-017-1809-7