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Fumito TANI Last modified date:2018.06.29



Graduate School
Undergraduate School


E-Mail
Homepage
http://tajigen.cm.kyushu-u.ac.jp/
home page of the lab .
Academic Degree
Doctor of Science
Country of degree conferring institution (Overseas)
No
Field of Specialization
Organic Chemistry
ORCID(Open Researcher and Contributor ID)
0000-0002-9166-2127
Total Priod of education and research career in the foreign country
00years00months
Outline Activities
Aromatic diimide compounds such as naphthalene diimide (NDI) and perylene diimide (PDI) have attracted much attention as electron acceptors, n-type semiconductors, chromophores in visible region and building blocks of supramolecular architectures. Besides NDI and PDI, tetracene diimide (TDI) is also expected to exhibit intriguing electronic and photophysical properties since TDI possesses linearly extended π-conjugated system. However, there have been only limited TDI derivatives reported in a few papers. Herein, we have designed a further π-extended TDI by fusing azulene as a 10π-conjugating unit. Azulene is a unique molecule, which has a dipole moment of about 1.08 D along the C2-C6 axis to afford electron-donating five-membered ring and electron-withdrawing seven-membered ring. Hence, bonding of five-membered ring of azulene to a diimide core is anticipated to realize effective donor-acceptor interaction and π-extension, leading to a smaller HOMO-LUMO gap and characteristic photophysical and electronic properties. TA-fused TDI exhibited four reversible one-electron reduction processes at –0.77, –1.08, –1.97, –2.12 V versus the Fc/Fc+ with a remarkable small HOMO-LUMO gap (0.96 eV). Absorption spectrum of TA-fused TDI exhibited intense absorption bands at 343, 410, 426, 600, 651 nm derived from TDI skeleton, and a broad low-energy band centered at 946 nm. The edge of the lowest-energy absorption band reached ca. 1400 nm corresponding to the energy gap of 0.89 eV, which is in good agreement with the electrochemical HOMO-LUMO gap. The Two-photon absorption (TPA) cross-section of TA-fused TDI was determined to be σ(2) = 2140 GM at 950 nm (1 GM = 10-50 cm4 s photon-1 molecule-1). The electron mobility of a thin film of TA-fused TDI prepared on an ITO /glass substrate was revealed to be μ = 1.7×10–4 cm2 V–1 s–1 by space charge limited current (SCLC) method.

Construction of functionalized nano space surrounded by large pai-electronic systems.
We have studied the supramolecular structures and photoelectronic properties of inclusion complexes of cyclic porphyrin dimers (M2-CPDPy, M=Ni, 2H) and fullerenes (C60, C70, PCBM ([6,6]-Phenyl-C61-butyric acid methyl ester) and Li+@C60). The porphyrin dimers have self-assembling 4-pyridyl groups at the meso positions and include fullerenes in their cavities with high affinities (Kassoc. ≈ 105 M-1). In crystals, C60⊂Ni2-CPDPy and PCBM⊂Ni2-CPDPy afford self-assembled porphyrin nanotubes containing the linear arrays of fullerene molecules. These self-assemblies are induced mainly by the non-classical hydrogen bonds between pyridyl nitrogens and porphyin β C-H groups. On the other hand, in the crystals of C60⊂H4-CPDPy and C70⊂H4-CPDPy, the included fullerene molecules show zigzag chains through van der Waals contacts with each other. Due to these well-ordered arrays of C60, both crystals of C60⊂Ni2-CPDPy and C60⊂H4-CPDPy have high charge mobilities (Σμ > 0.1 cm2V-1s-1). C60⊂H4-CPDPy shows photoinduced electron transfer from the porphyrin moieties to C60 and photovoltaic activity with IPCEmax=17 % in photoelectrochemical cells. Moreover, the inclusion complexes of lithium ion encapsulated C60 (Li+@C60) and M2-CPDPy exhibit photoinduced charge separation with very long lifetimes reaching submillisecond order.

Modeling study for cytochrome P450 by the use of synthetic heme complex to elucidate the oxygen activation mechanism of this enzyme family.
Research
Research Interests
  • Synthesis and photoelectronic properties of novel polycyclic pi-electron compounds
    keyword : pai-electron system, polycyclic,aromaticity
    2013.04~2023.03Synthesis and evaluation of functional compounds and supramolecular assemblies composed of porphyrins, phthalocyanines and fullerene.
  • Synthesis and evaluation of functional organic compounds and supramolecular assemblies including porphyrins, phthalocyanines and fullerenes
    keyword : porphyrin, phthalocyanine,fullerene,energy transfer,self-assembly,supramolecule, pai-electron system, electron transfer
    2002.04~2018.03Synthesis and evaluation of functional compounds and supramolecular assemblies composed of porphyrins, phthalocyanines and fullerene.
  • modeling of cytochrome P450
    keyword : porphyrin,catalyst,oxygen,oxidation,metalloenzyme,heme,P450,model,metal complex,
    1986.04~2007.12Modeling study to elucidate the mechanism of oxygen activation of cytochrome P450 by the use of synthetic heme complexes.
Academic Activities
Books
1. 谷 文都, Nobukuni, H, Sakaguchi, K., Kamimura, T., Chemical Science of π-Electron Systems, Springer, Japan, 423-442, 2015.10.
Reports
1. New reaction intermediates in oxygen activation by multinuclear copper complexes.
Papers
1. M. Narita, T. Murafuji, S. Yamashita, M. Fujinaga, K. Hiyama, Y. Oka, F. Tani, S. Kamijo, K. Ishiguro, Synthesis of 2-Iodoazulenes by the Iododeboronation of Azulen-2-ylboronic Acid Pinacol Esters with Copper(I) Iodide, J. Org. Chem., 83, 1298-1303, 2018.01.
2. H. Nishihara, T. Hirota, K. Matsuura, M. Ohwada, N. Hoshino, T. Akutagawa, T. Higuchi, H. Jinnai, Y. Koseki., H. Kasai., Y. Matsuo, J. Maruyama, Y. Hayasaka, H. Konaka., Y. Yamada, S. Yamaguchi, K. Kamiya, T. Kamimura, H. Nobukuni, Synthesis of ordered carbonaceous frameworks from organic crystals, Nature Commun., 10.1038/s41467-017-00152-z, 8, 2017.07,  東北大学多元物質科学研究所の西原洋知准教授、九州大学先導物質化学研究所の谷文都准教授、大阪産業技術研究所の丸山純研究主任、兵庫県立大学大学院工学研究科の松尾吉晃教授らを中心とする研究グループ)は、錯体結晶のように規則正しい骨格構造をもち、その中に金属原子が埋め込まれた新規炭素系触媒を開発しました。
 金属有機構造体を含む錯体結晶においては緻密な構造設計により高活性な触媒が開発されていますが、熱や薬品に弱いことや導電性が無いといった欠点がありました。金属を含有する炭素系触媒では反対に、熱や薬品に強く、導電性を持つ利点がありますが、構造が乱雑であるため活性を高くできないことが問題でした。今回の研究では、錯体結晶のように規則的な構造をもつ金属含有炭素系触媒の合成ルートを発見しました。本手法により、触媒活性を発現する化学構造を持ちながら、炭素材料の利点である耐熱性、耐薬品性、導電性を兼ね備えた新材料の合成が可能となるため、CO2転換触媒、燃料電池用の白金代替触媒をはじめとする様々な新規触媒の開発に繋がるものと期待されます。
 本成果は、平成29年7月24日(月)午前10時(イギリス時間)にNature Communication誌にてオンライン公開されました。.
3. M. Yamaji, S. Kato, K. Tomonari, M. Mamiya, 五島 健太, H. Okamoto, Y. Nakamura, 谷 文都, Blue Fluorescence from BF2 Complexes of N,O-Benzamide Ligands: Synthesis, Structure, and Photophysical Properties, Inorg. Chem., 10.1021/acs.inorgchem.7b02013, 2017.10.
4. T. Hamada, M. Hayasaki, H. Kitahara, K. Yamashita, A. Kariyazaki, 谷 文都, S. Onitsuka, H. Okamura, Essential oil composition of citrus peels in Kikai-jima Island, Japan, American Journal of Essential Oils and Natural Products, American Journal of Essential Oils and Natural Products, 5, 12-15, 2017.08.
5. S. Fujino, M. Yamaji, H. Okamoto, T. Mutai, I. Yoshikawa, H. Houjou, 谷 文都, Systematic investigations on fused π-system compounds of seven benzene rings prepared by photocyclization of diphenanthrylethenes, Photochem. Photobio. Sci., 16, 925-934, 2017.10.
6. Y. Ooyama, T. Enoki, J. Ohshita, T. Kamimura, S. Ozako, 小出 太郎, 谷 文都, Singlet oxygen generation properties of an inclusion complex of cyclic free-base porphyrin dimer and fullerene C60, RSC Adv., 7, 18690-18695, 2017.05.
7. M. Yamaji, Y. Hakoda, H. Okamoto, 谷 文都, Photochemical synthesis and photophysical properties of coumarins bearing extended polyaromatic rings studied by emission and transient absorption measurements, Photochem. Photobio. Sci., 16, 555-563, 2017.01.
8. K. Tani, H. Kato, N. Sakata, T. Yashima, K. Kubono, K. Hori, K. Tao, 五島 健太, 谷 文都, H. Takemura, K. Sakakibara, Y. Tsujii, Synthesis and Radical Polymerization of Acrylamides Having One or Two 3-Carbazolylmethyl Moieties and Properties of the Formed Polymers, Chem. Lett., 46, 85-87, 2017.01.
9. T. Koide, M. Takesue, T. Murafuji, K. Satomi, Y. Suzuki, J. Kawamata, K. Terai, M. Suzuki, H. Yamada, 塩田 淑仁, 吉澤 一成, 谷 文都, An Azulene-Fused Tetracene Diimide with a Small HOMO–LUMO Gap, ChemPlusChem, 10.1002/cplu.201600356, 2016.08.
10. Y. Shigeri, T. Kamimura, M. Ando, K. Uegaki,, H. Sato, 谷 文都, R. Arakawa, T. Kinumi, 2-Hydrazinoquinoline: a reactive matrix for matrix-assisted laser desorption/ionization mass spectrometry to detect gaseous carbonyl compounds, Eur. J. Mass Spectrom, 22, 83-90, 2016.07.
11. Y. Ooyama, K. Uenaka, T. Kamimura, S. Ozako, M. Kanda, T. Koide, 谷 文都, Dye-sensitized solar cell based on an inclusion complex of a cyclic porphyrin dimer bearing four 4-pyridyl groups and fullerene C60, RSC Adv., 6, 16150-16158, 2016.02.
12. 上村拓也, 大久保 敬, 川島雄樹, 尾迫秀和, 坂口健一, 福住俊一, 谷 文都, Long-Lived Photoinduced Charge Separation in Inclusion Complexes Composed of a Phenothiazine-Bridged Cyclic Porphyrin Dimer and Fullerenes, J. Phys. Chem. C, 119, 25634-25650, 2015.11.
13. 谷 文都, Kamimura, Takuya, Sakai, Hayato, Hasobe, Taku, Supramolecular photovoltaic cells utilizing inclusion complexes composed of Li+@C-60 and cyclic porphyrin dimer, JOURNAL OF PORPHYRINS AND PHTHALOCYANINES, 10.1142/S1088424614501156, 19, 1-3, 242-250, 2015.01.
14. 谷 文都, Kamimura, Takuya, Komura, Motonori, Komiyama, Hideaki, Iyoda, Tomokazu, Linear assembly of a porphyrin-C-60 complex confined in vertical nanocylinders of amphiphilic block copolymer films, CHEMICAL COMMUNICATIONS, 10.1039/c4cc09262g, 51, 9, 1685-1688, 2015.02.
15. 谷 文都, Sakatani, Shuhei, Kamimura, Takuya, Ohkubo, Kei, Fukuzumi, Shunichi, Synthesis and photodynamics of diphenylethynyl-bridged porphyrin-quinoidal porphyrin hybrids, JOURNAL OF PORPHYRINS AND PHTHALOCYANINES, 10.1142/S1088424614501144, 19, 1-3, 219-232, 2015.01.
16. 谷 文都, Kawai, Minoru, Yamaguchi, Takahide, Masaoka, Shigeyuki, Kohzuma, Takamitsu, Chiang, Linus, Storr, Tim, Mieda, Kaoru, Ogura, Takashi, Szilagyi, Robert K., Shimazaki, Yuichi, Influence of Ligand Flexibility on the Electronic Structure of Oxidized Ni-III-Phenoxide Complexes, INORGANIC CHEMISTRY, 10.1021/ic501181k, 53, 19, 10195-10202, 2014.10.
17. T. Kamimura, H. Nobukuni, 谷 文都, 坂口 健一, 尾迫秀和, 石田 真敏, 宇野 英満, 森 重樹, Phenothiazine-Bridged Cyclic Porphyrin Dimers as High-Affinity Hosts for Fullerenes and Linear Array of C60 in Self-Assembled Porphyrin Nanotube, J. Org. Chem., 79, 2980-2992, 2014.03.
18. K. Asami, A. Takashina, M. Kobayashi, 谷 文都, F. Thomas, Y. Shimazaki, S. Iwatsuki, T. Yajima, A. Kochem, M. van Gastel, T. Kohzuma, Characterization of one-electron oxidized copper(II)-salophen-type complexes; effects of electronic and geometrical structures on reactivities, Dalton Trans., 43, 2283-2293, 2014.01.
19. T. Kamimura, K. Ohkubo, Y. Kawashima, H. Nobukuni, 成田 吉徳, 谷 文都, S. Fukuzumi, Submillisecond-lived photoinduced charge separation in inclusion complexes composed of Li+@C60 and cyclic porphyrin dimers, Chem. Sci., 4, 4, 1451-1461, 2013.03.
20. K. Asami, K. Tsukidate, S. Iwatsuki, 谷 文都, 唐澤 悟, L. Chiang, T. Storr, F. Thomas, Y. Shimazaki, New Insights into the Electronic Structure and Reactivity of One-Electron Oxidized Copper(II)-(Disalicylidene)diamine Complexes, Inorg. Chem., 51, 22, 12450-12461, 2012.11.
21. M. Ishida, J. M. Lim, B. S. Lee, 谷 文都, J. L. Sessler, D. Kim, 成田 吉徳, Photophysical Analysis of 1,10-Phenanthroline-Embedded Porphyrin Analogues and Their Magnesium(II) Complexes, Chem. Eur. J., 18, 45, 14329-14341, 2012.11.
22. J. Nakazawa, J. Hagiwara, 島崎優一, 谷 文都, 成田 吉徳, Synthesis, Characterization, and Small Hydrocarbon Encapsulation of Dicavitand-Porphyrins, Bull. Chem. Soc. Jpn., 85, 8, 912-919, 2012.08.
23. Yuichi Shimazaki, Natsumi Arai, Tim J. Dunn, Tatsuo Yajima, Fumito Tani, Caterina F. Ramogida and Tim Storr, Influence of the chelate effect on the electronic structure of one-electron oxidized group 10 metal(II)-(disalicylidene)diamine complexes, Dalton Trans., 40, 11, 2469, 2011.04.
24. H. Nobukuni, Y. Shimazaki, H. Uno, Y. Naruta, K. Ohkubo, T. Kojima, S. Fukuzumi, S. Seki, H. Sakai, T. Hasobe, F. Tani, Supramolecular Structures and Photoelectronic Properties of the Inclusion Complex of a Cyclic Free-Base Porphyrin Dimer and C60, Chem. Eur. J., 16, 38, 11611, 2010.10.
25. M. Ishida, S. Karasawa, H. Uno, F. Tani, Y. Naruta, Protonation-Induced Formation of a Stable Singlet Biradicaloid Derived from a Modified Sapphyrin Analogue, Angew. Chem. Int. Ed., 49, 34, 5906, 2010.08.
26. M. Ishida, Y. Naruta, F. Tani, A Novel Porphyrin-related Macrocycle with an Embedded 1,10-Phenanthroline Moiety as a Fluorescent Mg (II) Ion Sensor, Angew. Chem. Int. Ed., 49, 1, 91-94, 2010.01.
27. H. Nobukuni, F. Tani, Y. Shimazaki, Y. Naruta, K. Ohkubo, T. Nakanishi, T. Kojima, S. Fukuzumi, S. Seki, Anisotropic High Electron Mobility and Photodynamics of a Self-Assembled Porphyrin Nanotube Including C60 Molecules, J. Phys. Chem. C, 113, 19694-19699, 2009.12.
28. Nobukuni, H; Shimazaki, Y; Tani, F; Naruta, Y, A nanotube of cyclic porphyrin dimers connected by nonclassical hydrogen bonds and its inclusion C-60 in a linear arrangement, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 46 (47): 8975-8978, 2007.12.
29. Y. Shimazaki, T. Nagano, H. Takesue, B. -H. Ye, F. Tani, Y. Naruta, Characterization of a Dinuclear MnV=O Complex and Its Efficient Evolution of O2 in the Presence of Water, Angew. Chem. Int. Ed., 10.1002/anie.200352564, 43, 1, 98-100, 43, 98-100., 2004.01.
30. J. -G. Liu, Y. Naruta, F. Tani, T. Chishiro, Y. Tachi, Formation and spectroscopic characterization of the dioxygen adduct of a heme-Cu complex possessing a cross-linked tyrosine-histidine mimic: modeling the active site of cytochrome c oxidase, Chem. Commun., 10.1039/b311538k, 1, 120-121, 120-121., 2004.01.
Presentations
1. Yuta Kawano, Taro Koide, Toshihiro Murafuji, Goto Kenta, Fumito Tani, Synthesis of novel porphycenes fused with azulene, International Symposium on Materials for Chemistry and Engineering (IMCE 2018), 2018.03.
2. Takaaki Teraoka, Toshihiro Murafuji, Kenta Goto, Fumito Tani, Synthesis and properties of azulene-fused isobenzothiophene helicenoids, International Symposium on Materials for Chemistry and Engineering (IMCE 2018), 2018.03.
3. Fumito Tani, Two Harvests from One Metalloporphyrin Complex, International Symposium on Materials for Chemistry and Engineering (IMCE 2018), 2018.03.
4. Masahiro Narita,Toshihiro Murafuji,Shin Kamijo,Katsuya Ishiguro,Yuji Mikata,Fumito Tani,Yoshihiro Matano, Synthesis, Structure and Properties of Dimesitylborylazulenes, 17th International Symposium on Novel Aromatics ( ISNA 2017), 2017.07.
5. Fumito Tani, An Azulene-Fused Tetracene Diimide with a Small HOMO-LUMO Gap, The 10th Taiwan-Japan Bilateral Symposium on Architecture of Functional Organic Molecules, 2017.10.
6. 谷 文都, Hirofumi Nobukuni, Ken-ichi Sakaguchi, Takuya Kamimura, Supramolecular structures and photoelectronic properties of inclusion complexes of self-assembling cyclic porphyrin dimers and fullerenes, KJF International Conference on Organic Materials for Electronics and Photonics 2016, 2016.09.
7. 谷 文都, Supramolecular structures and photoelectronic properties of iInclusion complexes of self-assembling cyclic porphyrin dimers and fullerenes, The 70th Fujihara Seminar, 2016.04.
8. 谷 文都, Hirotomo Nishihara, Takuya Kamimura, Masato Nishimura, Hideki Tanaka, Minoru T. Miyahara, Mao Owada, Takashi Kyotani, Induced-Fit Gas Uptake in Solids of Cyclic Porphyrin Dimers, 12th International Conference on the Fundamentals of Adsorption, 2016.05.
9. 谷 文都, Supramolecular Structures and Photoelectronic Properties of Inclusion Complexes of Self-Assembling Cyclic Porphyrin Dimers and Fullerenes, International Symposium on Construction and Application of Functional Molecules/Systems, 2015.10.
10. 谷 文都, Hirofumi NOBUKUNI, Ken-ichi SAKAGUCHI, Takuya KAMIMURA, Shuwa OZAKO, Supramolecular Structures and Photoinduced Charge Separation of Inclusion Complexes of Cyclic Porphyrin Dimers and Fullererenes, The 8th Taiwan-Japan Bilateral Symposium on Architecture of Functional Organic Molecules, 2014.11.
11. 谷 文都, 上村拓也, 大久保 敬, 川島 雄樹, 福住 俊一, 信国 浩文, 宇野 英満, 島崎優一, Supramolecular Structures and Photoelectronic Properties of Inclusion Complexes of Self-assembling Cyclic Porphyrin Dimers and Fullerenes, 15th International Symposium on Novel Aromatic Compounds, 2013.07.
12. 谷 文都, 上村拓也, 大久保 敬, 川島 雄樹, 福住 俊一, 信国 浩文, 宇野 英満, 島崎優一, Supramolecular Structures and Photoelectronic Properties of Inclusion Complexes of Self-assembling Cyclic Porphyrin Dimers and Fullerenes, 7th International Conference on Materials for Advanced Technologies, 2013.07.
13. 谷 文都, 上村拓也, 大久保 敬, 川島 雄樹, 福住 俊一, 信国 浩文, 成田 吉徳, Submillisecond-Lived Photoinduced Charge Separation in Inclusion Complexes Composed of Li+@C60 and Cyclic Porphyrin Dimers, 15th International Symposium on Novel Aromatic Compounds, 2013.07.
14. Fumito TANI, 信国浩文, 上村拓也, Yoshinori Naruta, 宇野英満, 島崎優一, Supramolecular Structures and Photoelectronic Properties of Inclusion Complexes of Cyclic Porphyrin Dimers and Fullerenes, The 7th International Conference on Molecular Electronics and Bioelectronics, 2013.03.
15. 上村拓也, 信国浩文, 宇野英満, 島崎優一, Yoshinori Naruta, 谷 文都, Supramolecular Structures of Inclusion Complexes of Fullerene C70 and Cyclic Porphyrin Dimers, The 7th International Conference on Porphyrins and Phthalocyanines, 2012.07.
16. 宇野英満, H. Watanabe, K. Tagawa, S. Mori, T. Okujima, 谷 文都, N. Komatsu, Selective porphyrin molecular tweezers for C60 and C70, The 7th International Conference on Porphyrins and Phthalocyanines, 2012.07.
17. Fumito TANI, 信国浩文, 上村拓也, 宇野英満, 島崎優一, Yoshinori Naruta, Supramolecular Structures of Inclusion Complexes of Cyclic Porphyrin Dimers and Fullerenes, The 7th International Conference on Porphyrins and Phthalocyanines, 2012.07.
18. 谷 文都, Supramolecular Structures of Inclusion Complexes of Cyclic Porphyrin Dimers and Fullerene PCBM, The 7th Japan-Taiwan Bilateral Symposium on Architecture of Functional Organic Molecules, 2012.10.
19. A Nanotube of Cyclic Porphyrin Dimers Connected by Nonclassical Hydrogen Bonds and Its Inclusion of Fullerene in a Linear Arrangement.
20. A Self-Assembled Nanotube of Cyclic Porphyrin Dimers and Its Inclusion of C60 in Linear Arrangement Affording Supramolecular Peapod.
21. A Nanotube of Cyclic Porphyrin Dimers Connected by Nonclassical Hydrogen Bonds and Its Inclusion of Fullerene in a Linear Arrangement.
22. Efficient intramolecular energy transfer of covalently-linked porphyrin-phthalocyanine hetero dimers.
23. A SELF-ASSEMBLED NANOTUBE OF CYCLIC PORPHYRIN DIMERS AND ITS INCLUSION OF C60 IN ONE-DIMENSIONAL ARRANGEMENT.
24. A Self-Assembled Nanotube of Cyclic Porphyrin Dimers and Its Inclusion of C60 in Linear Arrangement.
25. Organic nanotube of cyclic porphyrin dimer and its inclusion of C60.
26. Synthesis and efficient energy transfer of covalently-linked porphyrin-phthalocyanine hetero dimers.
27. Self-assembled structures of cyclic porphyrin dimer and trimer.
Awards
  • Supramolecular Structures of Inclusion Complexes of C70 and Cyclic Porphyrin Dimers
Educational
Educational Activities
Education for graduate and undergraduate students of Department of Chemistry in Faculty of Sciences and Graduate School of Sciences