Abstract
We have prepared nickel complexes and freebases of cyclic porphyrin dimers linked by butadiyne or phenothiazine groups. The porphyrin dimers have self-assembling pyridyl groups at the opposite meso positions and include fullerenes such as C60, PCBM, C70, and Li+@C60 to give π-complexes. In particular, the phenothiazine-bridged cyclic porphyrin dimers exhibit notable high affinities toward C60 (K assoc > 106 M−1) and C70 (K assoc > 107 M−1). In the crystal structures, the π-complexes of C60 and PCBM within the butadiyne-bridged nickel dimer and the phenothiazine-bridged freebase dimer afford self-assembled porphyrin nanotubes containing the linear arrays of the fullerenes. These self-assemblies are formed by the C-H · · · N hydrogen bonds and π-π interactions of the meso pyridyl groups. On the other hand, the π-complexes of C60 and C70 within the butadiyne-bridged freebase dimer gave the zigzag chains of the fullerenes through van der Waals contacts with each fullerene. These well-ordered C60 arrays yield high electron mobilities (Σμ > 10−1 cm2V−1 s−1). The π-complexes of C60 and Li+@C60 within the butadiyne-bridged dimers perform photoinduced electron transfer from the porphyrins to the fullerenes to give the CS states. The π-complexes of Li+@C60 with the butadiyne-bridged dimers afford the CS states of remarkably long lifetimes reaching submillisecond order.
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Acknowledgments
This work was supported by Grants-in-Aid (Scientific Research on Innovative Area “pi-Space” and the Global COE Program “Science for Future Molecular Systems”) from the Ministry of Education, Culture, Sports, Science and Technology of Japan; by the Cooperative Research Program of Network Joint Research Center for Materials and Devices of Institute for Materials Chemistry and Engineering, Kyushu University; and by Research Grants to F.T. from Tokuyama Science and Technology Foundation and Iketani Science and Technology Foundation. H.N. acknowledges the Japan Society for the Promotion of Science (JSPS) for a Research Fellowship for Young Scientists. We are sincerely grateful to our coworkers for their kind cooperation whose names appear as coauthors in our papers.
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Tani, F., Nobukuni, H., Sakaguchi, Ki., Kamimura, T. (2015). Supramolecular Structures and Photoelectronic Properties of π-Complexes Composed of Self-Assembling Cyclic Porphyrin Dimers and Fullerenes. In: Akasaka, T., Osuka, A., Fukuzumi, S., Kandori, H., Aso, Y. (eds) Chemical Science of π-Electron Systems. Springer, Tokyo. https://doi.org/10.1007/978-4-431-55357-1_25
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DOI: https://doi.org/10.1007/978-4-431-55357-1_25
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