単一指向性光伝達を可能とする光捕集錯体ナノシート・ナノワイヤ

• Project Area: Chemical conversion of solar energy by artificial photosynthesis: a breakthrough by fusion of related fields toward realization of practical processes
• Project/Area Number: 25107510
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: The University of Tokyo
• Principal Investigator: 坂本 良太 東京大学, 理学(系)研究科(研究院), 助教 (80453843)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2014: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000); Fiscal Year 2013: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: ナノシート / ナノワイヤ / ジピリン / 金属錯体 / 人工光合成

Outline of Annual Research Achievements

本年度は、ビス（ジピリナト）金属錯体ナノワイヤとナノシートの光捕集系としての利用価値の実証を行った。ナノワイヤに関しては、液液界面合成法による結晶性ナノワイヤ作成に成功した。このナノワイヤは適当な有機溶媒中で超音波することで繊維一本一本に剥離できる。実際に単離されたナノワイヤ繊維はAFMにより観察された。このナノワイヤとカーボンナノチューブと共役させた複合材料は、カーボンナノチューブ単独に比べより優れた熱電変換特性を示した。また、当該ナノワイヤを半導体透明電極に塗布することで、光電変換の活物質層として利用できることを見出した。以上の研究成果をChemical Science誌に論文として発表した。
ナノシートに関しては、界面合成法による大面積ナノシートの作成を達成した。液液界面法を用いることで厚さ6-800 nmのナノシート積層体を、センチメートルオーダーのドメインサイズにて合成できる。一方で、気液界面合成法を用いることで、単～数原子層ナノシートが合成でき、やはりこの種のナノシートとしては大きな、マイクロメートルオーダーのドメインサイズが実現できる。本ナノシートの構造決定をTEMの電子線回折により行った。本ナノシートについても光電変換材料への応用を行い、Nature Communications誌に論文を発表した。
一連の研究成果は、ビス（ジピリナト）金属錯体からなるナノワイヤ・ナノシートが人工光合成光捕集系として利用できる可能性を示すものである。

Research Progress Status

26年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

26年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Electron Transport Dynamics in Redox-Molecule-Terminated Branched Oligomer Wires on Au(111) (2015)
  • Author(s): Ryota Sakamoto, Shunsuke Katagiri, Hiroaki Maeda, Yoshihiko Nishimori, Seiji Miyashita, Hiroshi Nishihara
  • Journal Title: J. Am. Chem. Soc. Volume: 137 Issue: 2 Pages: 734-741
  • DOI: 10.1021/ja509470w
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] A photofunctional bottom-up bis(dipyrrinato)zinc(II) complex nanosheet (2015)
  • Author(s): Ryota Sakamoto, Ken Hoshiko, Qian Liu, Toshiki Yagi, Tatsuhiro Nagayama, Shinpei Kusaka, Mizuho Tsuchiya, Yasutaka Kitagawa, Wai-Yeung Wong, Hiroshi Nishihara
  • Journal Title: Nature Commun. 2015, 6, Volume: 6 Issue: 1 Pages: 6713-6713
  • DOI: 10.1038/ncomms7713
  • Peer Reviewed / Open Access
• [Journal Article] Bis(dipyrrinato)metal(II) coordination polymers: Crystallization, exfoliation into single wires, and electric conversion ability (2015)
  • Author(s): Ryota Matsuoka, Ryojun Toyoda, Ryota Sakamoto, Mizuho Tsuchiya, Ken Hoshiko, Tatsuhiro Nagayama, Yoshiyuki Nonoguchi, Kunihisa Sugimoto, Eiji Nishibori, Tsuyoshi Kawai, Hiroshi Nishihara
  • Journal Title: Chemical Science Volume: in press Issue: 5 Pages: 2853-2858
  • DOI: 10.1039/c5sc00273g
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Electrochromic Bis(terpyridine)Iron(II) Complex Nanosheets (2015)
  • Author(s): Kenji Takada, Ryota Sakamoto, Shi-Ting Yi, Shunsuke Katagiri, Tetsuya Kambe, Hiroshi Nishihara
  • Journal Title: J. Am. Chem. Soc. Volume: 137 Issue: 14 Pages: 4681-4689
  • DOI: 10.1021/ja510788b
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Heteroleptic bis(dipyrrinato)copper(II) and nickel(II) complexes (2015)
  • Author(s): Ryojun Toyoda, Mizuho Tsuchiya, Ryota Sakamoto, Ryota Matsuoka, Kuo-Hui Wu, Yohei Hattori, Hiroshi Nishihara
  • Journal Title: Dalton Transactions Volume: in press Issue: 34 Pages: 15103-15106
  • DOI: 10.1039/c5dt00724k
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis, Characterization, and Physical Properties of Oligo(1-(N,N-dimethylamino)pyrrole)s and Their Doped Forms, Precursors of Candidates for Molecular Flat-band Ferromagnets (2015)
  • Author(s): Y. Yamanoi, K. Takahashi, T. Hamada, N. Ohshima, M. Kurashina, Y. Hattori, T. Kusamoto, R. Sakamoto, M. Miyachi, and H. Nishihara
  • Journal Title: Journal of Materials Chemistry C Volume: 3 Issue: 17 Pages: 1-1
  • DOI: 10.1039/c4tc02941k
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] π-Conjugated bis(terpyridine)metal complex molecular wires (2015)
  • Author(s): Ryota Sakamoto, Wu Kuo-Hui, Ryota Matsuoka, Hiroaki Maeda, Hiroshi Nishihara
  • Journal Title: Chem. Soc. Rev. Volume: in press Issue: 21 Pages: 7698-7714
  • DOI: 10.1039/c5cs00081e
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Meso-N-arylamino- and N,N-diarylaminoporphyrinoids: Syntheses, Properties, and Applications (2015)
  • Author(s): Ryota Sakamoto, Suzaliza Mustafar, Hiroshi Nishihara
  • Journal Title: J. Porphyr. Phthalocya. Volume: 19 Issue: 01-03 Pages: 21-31
  • DOI: 10.1142/s1088424615500091
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Acid-Responsive Fluorescent Compounds Based on Nitro-Group-Substituted L-Shaped Pentacycles, Pyrrolo[1,2-a][1,8]naphthyridines (2014)
  • Author(s): Kotaro Tateno, Rie Ogawa, Ryota Sakamoto, Mizuho Tsuchiya, Takashi Otani, Takao Saito
  • Journal Title: Org. Lett. Volume: 16 Issue: 12 Pages: 3212-3215
  • DOI: 10.1021/ol501226x
  • Peer Reviewed
• [Journal Article] Redox Control and High Conductivity of Nickel Bis(dithiolene) Complex π–Nanosheet: A Potential Organic Two-Dimensional Topological Insulator (2014)
  • Author(s): T. Kambe, R. Sakamoto, T. Kusamoto, T. Pal, N. Fukui, K. Hoshiko, T. Shimojima, Z. Wang, K. Ishizaka, S. Hasegawa, F. Liu, and H. Nishihara
  • Journal Title: Journal of the American Chemical Society Volume: 136 Issue: 41 Pages: 14357-14360
  • DOI: 10.1021/ja507619d
  • Peer Reviewed
• [Journal Article] Crystal structure of (Z)-1-(ferrocenylethynyl)-10-(phenylimino)anthracen-9(10H)-one fromsynchrotron X-ray powder diffraction (2014)
  • Author(s): Eiji Nishibori, Shinobu Aoyagi, Makoto Sakata, Ryota Sakamoto, Hiroshi Nishihara
  • Journal Title: Acta Cryst. Volume: E70 Pages: 573-576
  • Peer Reviewed
• [Journal Article] Ordered Alignment of a One-Dimensional π-Conjugated Nickel Bis(dithiolene) Complex Polymer Produced via a Liquid-Liquid Interfacial Reaction (2014)
  • Author(s): Ryota Matsuoka, Ryota Sakamoto, Tetsuro Kusamoto, Tetsuya Kambe, Kenji Takada, Hiroshi Nishihara
  • Journal Title: Chemical Communications Volume: 50 Issue: 60 Pages: 8137-8139
  • DOI: 10.1039/c4cc02022g
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Asymmetric dinuclear bis (dipyrrinato) Zinc (II) complexes : Broad absorption and unidirectional quantitative exciton transmission (2014)
  • Author(s): Mizuho Tsuchiya, Ryota Sakamoto, Shinpei Kusaka, Yasutaka Kitagawa, Mitsutaka Okumura, Hiroshi Nishihara
  • Journal Title: Chemical Communications Volume: (In press) Issue: 44 Pages: 5881-5883
  • DOI: 10.1039/c4cc01573h
  • Peer Reviewed
• [Journal Article] Luminescent Heteroleptic Tris (dipyrrinato) indium (III) Complexes (2014)
  • Author(s): Shinpei Kusaka, Ryota Sakamoto, Hiroshi Nishihara
  • Journal Title: Inorganic Chemistry Volume: 53 Issue: 7 Pages: 3275-3277
  • DOI: 10.1021/ic500326u
  • Peer Reviewed
• [Journal Article] Reactivity and Electronic Properties of a Ferrocene Molecule Bearing an N,C-chelate BMes2 Unit (2014)
  • Author(s): Yingli Rao, Tetsuro Kusamoto, Ryota Sakamoto, Hiroshi Nishihara, Suning Wang
  • Journal Title: Organometallics Volume: 33 Issue: 7 Pages: 1787-1793
  • DOI: 10.1021/om500138f
  • Peer Reviewed
• [Journal Article] Surface Junction Effects on Interfacial Electron Transfer Between Bis (terpyridine) iron (II) and Hdrogen-Terminated Silicon (111) Electrode (2014)
  • Author(s): Hiroaki Maeda, Ryota Sakamoto, Hiroshi Nishihara
  • Journal Title: Chem. Eur. J. Volume: 20 Issue: 10 Pages: 2761-2764
  • DOI: 10.1002/chem.201304588
  • Peer Reviewed
• [Journal Article] Fabrication of Dense and Multi-layered Films of The Nickel Bis (dithiolene) Nanosheet By Means of The Langmuir-Schafer Method (2014)
  • Author(s): K. Hoshiko, Tetsuya Kambe, R. Sakamoto, K. Takada, and H. Nishihara
  • Journal Title: Chem. Lett. Volume: 43 Issue: 2 Pages: 252-253
  • DOI: 10.1246/cl.130882
  • NAID: 130004867969
  • Peer Reviewed
• [Journal Article] Comparative Study of Photochromic Ferrocene-conjugated Dimethyldihydropyrene Derivatives (2013)
  • Author(s): Satoshi Muratsugu, Masa-aki Kishida, Ryota Sakamoto, Hiroshi Nishihara
  • Journal Title: Chem. Eur. J. Volume: 19 Issue: 51 Pages: 17314-17327
  • DOI: 10.1002/chem.201303456
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] π-Conjugated Trinuclear Group-9 Metalladithiolenes with a Triphenylene Backbone (2013)
  • Author(s): R. Sakamoto, Tetsuya Kambe, S. Tsukada, K. Takada, K. Hoshiko, Y. Kitagawa, M. Okumura, H. Nishihara
  • Journal Title: Inorg. Chem. Volume: 52 Issue: 13 Pages: 7411-7416
  • DOI: 10.1021/ic400110z
  • Peer Reviewed
• [Journal Article] 1,4-Bis(4-ferrocenylphenylethynyl)anthraquinone by synchrotron X-ray powder diffraction (2013)
  • Author(s): Maki Sachiko, Eiji Nishibori, Masanori Yoshida, Shinobu Aoyagi, Makoto Sakata, Masaki Takata, Mio Kondo, Masaki Murata, Ryota Sakamoto, Hiroshi Nishihara
  • Journal Title: Acta. Cryst. Volume: C69 Issue: 7 Pages: 696-703
  • DOI: 10.1107/s0108270113013978
  • Peer Reviewed
• [Journal Article] A bis (terpyridine) iron network polymer on carbon for a potential energy storage material (2013)
  • Author(s): Kuo-Hui Wu, Hiroaki Maeda, Tetsuya Kambe, Ken Hoshiko, Eunice Jia Han Phua, Ryota Sakamoto, Hiroshi Nishihara
  • Journal Title: Dalton Trans. Volume: 42 Issue: 45 Pages: 15877-15880
  • DOI: 10.1039/c3dt51186c
  • Peer Reviewed
• [Journal Article] Intramolecular [2+2+2] cycloaddition of bis(propargylphenyl)​carbodiimides: synthesis of L-​shaped π-​extended compounds with pyrrolo[1,​2-​a]​[1,​8]​naphthyridine corner units (2013)
  • Author(s): T. Otani, T. Saito, R. Sakamoto, H. Osada, A. Hirahara, N. Furukawa, N. Kutsumura, T. Matsuo, K. Tamao
  • Journal Title: Chem. Commun. Volume: 49 Issue: 55 Pages: 6206-6208
  • DOI: 10.1039/c3cc42792g
  • Peer Reviewed
• [Journal Article] Orthogonal bis (terpyridine)-Fe (II) metal complex wires on a tripod scaffold : Rapid electron transport (2013)
  • Author(s): Ryota Sakamoto, Yuuki Ohirabaru, Ryota Matsuoka, Hiroaki Maeda, Shunsuke Katagiri, Hiroshi Nishihara
  • Journal Title: Chem. Commun. Volume: 49 Issue: 64 Pages: 7108-7110
  • DOI: 10.1039/c3cc42478b
  • Peer Reviewed
• [Journal Article] Metal Complex Oligomer and Polymer Wires on Electrodes : Tactical Constructions and Versatile Functionalities (2013)
  • Author(s): Hiroaki Maeda, Ryota Sakamoto, Hiroshi Nishihara
  • Journal Title: Polymer Volume: 54 Issue: 17 Pages: 4383-4403
  • DOI: 10.1016/j.polymer.2013.04.019
  • Peer Reviewed
• [Presentation] 金属錯体低次元系の構築と物性 (2015)
  • Author(s): 坂本 良太
  • Organizer: 第2回東北大学リーディング大学院研究会「金属錯体の固体物性最前線‐金属錯体と固体物性物理と生物物性の連携新領域をめざして‐」
  • Place of Presentation: 仙台（宮城）
  • Year and Date: 2015-02-20 – 2015-02-22
  • Invited
• [Presentation] Bottom-up molecular wires and sheets for artificial photosynthesis (2014)
  • Author(s): Ryota Sakamoto
  • Organizer: 2014 International Conference on Artificial Photosynthesis (ICARP2014)
  • Place of Presentation: 淡路（兵庫）
  • Year and Date: 2014-11-24 – 2014-11-28
  • Invited
• [Presentation] Functional Bottom-Up Metal Complex Nanosheets (2014)
  • Author(s): Ryota Sakamoto
  • Organizer: Vietnam Malaysia International Chemical Congress (VMICC)
  • Place of Presentation: ハノイ（ベトナム）
  • Year and Date: 2014-11-06 – 2014-11-09
  • Invited
• [Presentation] Functional Bottom-Up Metal Complex Nanosheets (2014)
  • Author(s): Ryota Sakamoto
  • Organizer: 18th Malaysian International Chemical Congress (18MICC)
  • Place of Presentation: クアラルンプール（クアラルンプール）
  • Year and Date: 2014-11-03 – 2014-11-05
  • Invited
• [Presentation] Brightly Luminescent π-Extended Dipyrrin Complexes (2014)
  • Author(s): Ryota Sakamoto, Shinpei Kusaka, Mizuho Tsuchiya, Hiroshi Nishihara
  • Organizer: 41st International Conference on Coordination Chemistry (ICCC-41)
  • Place of Presentation: シンガポール（シンガポール）
  • Year and Date: 2014-07-21 – 2014-07-25
  • Invited
• [Presentation] Metal Complex Nanowires and Nanosheets Aiming at Photosynthetic Antenna Models (2014)
  • Author(s): Ryota Sakamoto
  • Organizer: Tenth International Workshop on Supramolecular Nanoscience of Chemically Programmed Pigments (SNCPP14)
  • Place of Presentation: 草津（滋賀）
  • Year and Date: 2014-05-30 – 2014-05-31
  • Invited
• [Presentation] 光機能性「ボトムアップ型」金属錯体ナノシート・ナノワイヤ (2014)
  • Author(s): 坂本 良太
  • Organizer: 日本化学会研究会「低次元系光機能材料研究会」第３回研究講演会―低次元系光機能材料と人工光合成
  • Place of Presentation: 東京（東京）
  • Year and Date: 2014-05-09
  • Invited
• [Presentation] Coordination Programming of Functional Molecular Wires and Sheets (2014)
  • Author(s): Ryota Sakamoto
  • Organizer: Asian International Symposium in The 94th Annual Meeting
  • Place of Presentation: 名古屋（愛知）
  • Year and Date: 2014-03-21 – 2014-03-25
  • Invited
• [Presentation] 「ボトムアップ型」金属錯体ナノシート・ナノワイヤ」 (2014)
  • Author(s): 坂本 良太
  • Organizer: 第１回東北大学リーディング大学院研究会「金属錯体の固体物性最前線‐金属錯体と固体物性物理と生物物性の連携新領域をめざして‐」
  • Place of Presentation: 仙台（宮城）
  • Year and Date: 2014-02-19 – 2014-02-21
  • Invited
• [Presentation] Coordination Programming of Photo- and Electro-Functional Molecular Assemblies (2013)
  • Author(s): Ryota Sakamoto, Yoshinori Yamanoi, Hiroshi Nishiahra
  • Organizer: 15th Asian Chemical Congress 2013 (15 ACC)
  • Place of Presentation: シンガポール（シンガポール）
  • Year and Date: 2013-08-21 – 2013-08-23
  • Invited
• [Presentation] Coordination Programming of Photo- and Electro-Functional Molecular Assemblies (2013)
  • Author(s): Ryota Sakamoto
  • Organizer: Japan-China young scientist symposium "Frontier of coordination chemistry at the interface of nano and micro
  • Place of Presentation: 岡崎（愛知）
  • Year and Date: 2013-06-13 – 2013-06-15
  • Invited