光捕集ジピリン金属錯体ナノシート・ナノワイヤ：化学エネルギー変換系との融合

• 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: 15H00862
• 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, 大学院理学系研究科(理学部), 助教 (80453843)
• Project Period (FY): 2015-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2016: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000); Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: ジピリン / ナノシート / ナノワイヤ / 人工光合成 / 光捕集系 / 金属錯体 / 低次元系 / ジピリン錯体 / 亜鉛

Outline of Annual Research Achievements

ジピリン亜鉛錯体は自発的な分子集合体生成, 可視・近赤外における強発光・強吸収など人工「光捕集系」の構築に有利な特性を有するが, 実際の応用例は存在しない. 本研究課題では前2年間の公募研究成果を更に発展させ人工「光捕集系」を完成することを目的に設定した. 一次元ジピリン金属錯体ナノワイヤについては, らせん構造を有するものをジピリン配位子から設計・合成した. 得られたナノワイヤは単一繊維一本一本に剥離することができ, AFMにて観察できる. また, らせん構造によりナノワイヤの分散液は, 円偏光発光強度が対応するジピリン単核錯体に比べ7倍程度の増幅を示した. 二次元ジピリン金属錯体ナノシートに関して, 2015年に報告した光電変換機能の増強を目指した. 具体的にはポルフィリンをコアとして有するジピリン４量体配位子を設計・合成し, これと亜鉛イオンから構築される碁盤格子ナノシートの構築を行った. 碁盤格子ナノシートの光電変換量子収率は２倍強増幅され, また応答波長も450-550 nmから400-650 nmへと, 可視全領域がカバーされるまでに拡張された. この他, 中心金属に亜鉛を有するテルピリジン金属錯体ナノシートの合成を行った. この二次元ナノシートは紫外光励起により青色発光を示すとともに, カチオン性の骨格に由来するアニオン性ゲストの包摂挙動を示した. アニオン性色素をゲストとして取り込むことで, ホストであるナノシートからゲスト分子への定量的な励起子移動を示すことを見出した. この特性は人工光合成の光捕集系として利用できるものである.

Research Progress Status

28年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

28年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] Hong Kong Baptist University/Hong Kong Polytechnic University(中国香港)
• [Int'l Joint Research] Universitaet Bremen(ドイツ)
• [Journal Article] Coordination Nanosheets Based on Terpyridine-zinc(II) complexes: As Photoactive Host Materials (2017)
  • Author(s): Takamasa Tsukamoto, Kenji Takada, Ryota Sakamoto, 他18名
  • Journal Title: J. Am. Chem. Soc. Volume: 139 Issue: 15 Pages: 5359-5366
  • DOI: 10.1021/jacs.6b12810
  • Peer Reviewed
• [Journal Article] Photofunctionality in Porphyrin-Hybridized Bis(dipyrrinato)zinc(II) Complex Micro- and Nanosheets (2017)
  • Author(s): *Ryota Sakamoto, Toshiki Yagi, Ken Hoshiko, Shinpei Kusaka, Ryota Matsuoka, Hiroaki Maeda, Zheng Liu, Qian Liu, *Wai-Yeung Wong, *Hiroshi Nishihara
  • Journal Title: Angew. Chem. Int. Ed. Volume: 56 Issue: 13 Pages: 3526-3530
  • DOI: 10.1002/anie.201611785
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Crystalline Graphdiyne Nanosheets Produced at a Gas/Liquid or Liquid/Liquid Interface (2017)
  • Author(s): Ryota Matsuoka, *Ryota Sakamoto, Ken Hoshiko, Sono Sasaki, Hiroyasu Masunaga, Kosuke Nagashio, *Hiroshi Nishihara
  • Journal Title: J. Am. Chem. Soc. Volume: 139 Issue: 8 Pages: 3145-3152
  • DOI: 10.1021/jacs.6b12776
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] A simple zinc(II) complex that features multi‐functional luminochromism induced by reversible ligand dissociation (2017)
  • Author(s): Takamasa Tsukamoto, Risa Aoki, Ryota Sakamoto, Ryojun Toyoda, Masaki Shimada, Yohei Hattori, Mizuki Asaoka, Yasutaka Kitagawa, Eiji Nishibori, Masayoshi Nakano, Hiroshi Nishihara
  • Journal Title: Chem. Commun. Volume: 53 Issue: 26 Pages: 3657-3660
  • DOI: 10.1039/c6cc10190a
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Interfacial synthesis of electrofunctional coordination nanowires and nanosheets of bis(terpyridine) complexes (2017)
  • Author(s): Hiroaki Maeda, Ryota Sakamoto, *Hiroshi Nishihara
  • Journal Title: Coord. Chem. Rev. Volume: 印刷中 Pages: 139-149
  • DOI: 10.1016/j.ccr.2017.02.013
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Bis(dipyrrinato)zinc(II) Complex Chiroptical Wires: Exfoliation into Single Strands and Intensification of Circularly Polarized Luminescence (2017)
  • Author(s): Aoki Risa、Toyoda Ryojun、Koegel Julius F.、Sakamoto Ryota、Kumar Jatish、Kitagawa Yasutaka、Harano Koji、Kawai Tsuyoshi、Nishihara Hiroshi
  • Journal Title: Journal of the American Chemical Society Volume: 139 Issue: 45 Pages: 16024-16027
  • DOI: 10.1021/jacs.7b07077
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Mechano-, thermo-, solvato-, and vapochromism in bis(acetato-κ1O)[4′-(4-(diphenylamino)phenyl)](2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)zinc(ii) and its polymer (2017)
  • Author(s): Tsukamoto Takamasa、Aoki Risa、Sakamoto Ryota、Toyoda Ryojun、Shimada Masaki、Hattori Yohei、Kitagawa Yasutaka、Nishibori Eiji、Nakano Masayoshi、Nishihara Hiroshi
  • Journal Title: Chemical Communications Volume: 53 Issue: 70 Pages: 9805-9808
  • DOI: 10.1039/c7cc05022d
  • Peer Reviewed
• [Journal Article] β-IminoBODIPY oligomers: facilely accessible π-conjugated luminescent BODIPY arrays (2017)
  • Author(s): Tsuchiya Mizuho、Sakamoto Ryota、Shimada Masaki、Yamanoi Yoshinori、Hattori Yohei、Sugimoto Kunihisa、Nishibori Eiji、Nishihara Hiroshi
  • Journal Title: Chemical Communications Volume: 53 Issue: 54 Pages: 7509-7512
  • DOI: 10.1039/c7cc03279j
  • Peer Reviewed
• [Journal Article] Coordination nanosheets (CONASHs): strategies, structures and functions (2017)
  • Author(s): Sakamoto Ryota、Takada Kenji、Pal Tigmansu、Maeda Hiroaki、Kambe Tetsuya、Nishihara Hiroshi
  • Journal Title: Chemical Communications Volume: 53 Issue: 43 Pages: 5781-5801
  • DOI: 10.1039/c7cc00810d
  • Peer Reviewed
• [Journal Article] Bis(dipyrrinato)zinc(II) Complexes: Emission in the Solid State (2016)
  • Author(s): M. Tsuchiya, R. Sakamoto, M. Shimada, Y. Yamanoi, Y. Hattori, K. Sugimoto, E. Nishibori, H. Nishihara
  • Journal Title: Inorg. Chem. Volume: 55 Issue: 12 Pages: 5732-5734
  • DOI: 10.1021/acs.inorgchem.6b00431
  • Peer Reviewed
• [Journal Article] Electron Transport of Bis(terpyridine)iron(II) Complex Wire on a Semiconducting Electrode (2016)
  • Author(s): Hiroaki Maeda, Ryota Sakamoto, Hiroshi Nishihara
  • Journal Title: J. Electroanal. Chem. Volume: 779 Pages: 112-116
  • DOI: 10.1016/j.jelechem.2016.04.027
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Dissymmetric Bis(dipyrrinato)zinc(II) Complexes: Rich Variety and Bright Red to Near-Infrared Luminescence with a Large Pseudo Stokes Shift (2016)
  • Author(s): Ryota Sakamoto, Toshiki Iwashima, Julius F. Kögel, Shinpei Kusaka, Mizuho Tsuchiya, Yasutaka Kitagawa, Hiroshi Nishihara
  • Journal Title: J. Am. Chem. Soc. Volume: 138 Issue: 17 Pages: 5666-5677
  • DOI: 10.1021/jacs.6b02128
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Heteroleptic [Bis (oxazoline)](dipyrrinato) zinc (II) Complexes: Bright and Circularly Polarized Luminescence from an Originally Achiral Dipyrrinato Ligand (2016)
  • Author(s): Julius F Kogel, Shinpei Kusaka, Ryota Sakamoto, Toshiki Iwashima, Mizuho Tsuchiya, Ryojun Toyoda, Ryota Matsuoka, Takamasa Tsukamoto, Junpei Yuasa, Yasutaka Kitagawa, Tsuyoshi Kawai, Hiroshi Nishihara
  • Journal Title: Angewandte Chemie International Edition Volume: 55 Issue: 4 Pages: 1377-1381
  • DOI: 10.1002/anie.201509411
  • Peer Reviewed
• [Journal Article] Bright Solid-State Emission of Disilane-Bridged Donor-Acceptor-Donor and Acceptor-Donor-Acceptor Chromophores (2016)
  • Author(s): M. Shimada, M. Tsuchiya, R. Sakamoto, Y. Yamanoi, E. Nishibori, K. Sugimoto, H. Nishihara
  • Journal Title: Angew. Chem. Int. Ed. Volume: 55 Issue: 9 Pages: 3022-3026
  • DOI: 10.1002/anie.201509380
  • Peer Reviewed
• [Journal Article] Electrochemical fabrication of one-dimensional porphyrinic wires on electrodes (2016)
  • Author(s): Suzaliza Mustafar, Kuo-Hui Wu, Ryojun Toyoda, Kenji Takada, Hiroaki Maeda, Mariko Miyachi, Ryota Sakamoto, Hiroshi Nishihara
  • Journal Title: Inorg. Chem. Front. Volume: 3 Issue: 3 Pages: 370-375
  • DOI: 10.1039/c5qi00239g
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] The coordination nanosheet (CONASH) (2016)
  • Author(s): Ryota Sakamoto, Kenji Takada, Xinsen Sun, Tigmansu Pal, Takamasa Tsukamoto, Eunice Jia Han Phua, Amalia Rapakousiou, Ken Hoshiko, Hiroshi Nishihara
  • Journal Title: Coord. Chem. Rev. Volume: 未決定 Pages: 118-128
  • DOI: 10.1016/j.ccr.2015.12.001
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Coordination Programming of Two-dimensional Metal Complex Frameworks (2016)
  • Author(s): Hiroaki Maeda, Ryota Sakamoto, Hiroshi Nishihara
  • Journal Title: Langmuir Volume: 32 Issue: 11 Pages: 2527-2538
  • DOI: 10.1021/acs.langmuir.6b00156
  • 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] Interfacial Synthesis of Electrically Palladium Bis(dithiolene) Complex Nanosheet (2015)
  • Author(s): Tigmansu Pal, Mao Lin Foo, Tetsuro Kusamoto, Tetsuya Kambe, Ryota Matsuoka, Ryota Sakamoto, Hiroshi Nishihara
  • Journal Title: ChemPlusChem Volume: 80 Issue: 8 Pages: 1255-1258
  • DOI: 10.1002/cplu.201500206
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Bis(terpyridine)iron(II) Complex Wires with a Bithiophene Linker for Superior Long Range Electron Transport (2015)
  • Author(s): Aayushi Bajpayee, Hiraoki Maeda, Shunsuke Katagiri, Ryota Sakamoto, Hiroshi Nishihara
  • Journal Title: Chem. Lett. Volume: 44 Issue: 9 Pages: 1211-1213
  • DOI: 10.1246/cl.150519
  • NAID: 130005096880
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Rapid Electron Transport Phenomenon in the Bis(terpyridine)metal Complex Wire: Marcus Theory and Electrochemical Impedance Spectroscopy Study (2015)
  • Author(s): Ryota Sakamoto, Hiroaki Maeda, Hiroshi Nishihara
  • Journal Title: J. Phys. Chem. Lett. Volume: 6 Issue: 19 Pages: 3821-3826
  • DOI: 10.1021/acs.jpclett.5b01725
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] New aspects in bis and tris(dipyrrinato)metal complexes: bright luminescence, self-assembled nanoarchitectures, and materials applications (2015)
  • Author(s): Ryota Sakamoto, Toshiki Iwashima, Tsuchiya Mizuho, Ryojun Toyoda, Ryota Matsuoka, Julius F. Koegel, Shinpei Kusaka, Ken Hoshiko, Toshiki Yagi, Tatsuhiro Nagayama, Hiroshi Nishihara
  • Journal Title: J. Mater. Chem. A Volume: 3 Issue: 30 Pages: 15357-15371
  • DOI: 10.1039/c5ta02040a
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Presentation] 金属錯体を基盤とする機能性低次元系のボトムアップ創製 (2016)
  • Author(s): 坂本 良太
  • Organizer: 日本化学会 第96春季年会
  • Place of Presentation: 同志社大学京田辺キャンパス（京都府京田辺市）
  • Year and Date: 2016-03-25
  • Invited
• [Presentation] 有機ー無機ハイブリッドナノシートのボトムアップ合成と機能性ナノ材料への応用 (2016)
  • Author(s): 坂本 良太
  • Organizer: 日本物理学会 第71回年次大会
  • Place of Presentation: 宮城学院大学（宮城県仙台市）
  • Year and Date: 2016-03-19
  • Invited
• [Presentation] New Aspects in Dipyrrin-Metal Complexes: From Molecular Science to Low-Dimensional Molecular Assemblies (2016)
  • Author(s): Ryota Sakamoto
  • Organizer: International Symposium on Pure & Applied Chemistry (ISPAC) 2016
  • Int'l Joint Research / Invited
• [Presentation] Functional "bottom-up" metal complex nanosheets (2016)
  • Author(s): Ryota Sakamoto
  • Organizer: 2016 Kumamoto Symposium on Two Dimensional Nanomaterials (2016KST)
  • Place of Presentation: 熊本大学黒髪キャンパス（熊本県熊本市）
  • Invited
• [Presentation] A photofunctional “bottom-up” bis(dipyrrinato)zinc(II) complex nanosheet (2015)
  • Author(s): Ryota Sakamoto
  • Organizer: The 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem)
  • Place of Presentation: アメリカ合衆国（ホノルル）
  • Year and Date: 2015-12-15
  • Invited
• [Presentation] Photofunctional bis(dipyrrinato)metal complex nanowire and nanosheet (2015)
  • Author(s): Ryota Sakamoto
  • Organizer: 1st International Caparica Christmas Congress on Translational Chemistry
  • Place of Presentation: ポルトガル（コスタダカパリカ）
  • Year and Date: 2015-12-04
  • Invited
• [Presentation] Functional "bottom-up" metal complex nanosheets (2015)
  • Author(s): Ryota Sakamoto
  • Organizer: International Conference on Small Science (ICSS 2015)
  • Place of Presentation: タイ（プーケット）
  • Year and Date: 2015-11-13
  • Invited
• [Presentation] LOW-DIMENSIOANAL MATERIALS BASED ON COORDINATION COMPOUNDS (2015)
  • Author(s): Ryota Sakamoto
  • Organizer: 10th China-Japan Joint Symposium on Metal Cluster Compounds (CJSMCC-2015)
  • Place of Presentation: 中国（福州）
  • Year and Date: 2015-10-23
  • Invited
• [Presentation] 金属錯体を基盤とする機能性低次元系の創製 (2015)
  • Author(s): 坂本 良太
  • Organizer: 第65回錯体化学討論会
  • Place of Presentation: 奈良女子大学（奈良県奈良市）
  • Year and Date: 2015-09-25
  • Invited
• [Presentation] Photofunctional bis(dipyrrinato)metal complex nanowire and nanosheet (2015)
  • Author(s): Ryota Sakamoto
  • Organizer: The 2nd Japan-Germany Joint Symposium on Coordination Chemistry,
  • Place of Presentation: 奈良女子大学（奈良県奈良市）
  • Year and Date: 2015-09-23
  • Invited
• [Presentation] 異種界面を利用した機能性「ボトムアップ型」ナノシートの創成 (2015)
  • Author(s): 坂本 良太
  • Organizer: 第64回高分子討論会
  • Place of Presentation: 東北大学片平キャンパス（宮城県仙台市）
  • Year and Date: 2015-09-22
  • Invited
• [Presentation] A photofunctional bottom-up bis(dipyrrinato)zinc(II) complex nanosheet (2015)
  • Author(s): Ryota Sakamoto
  • Organizer: 4th International Symposium on Energy Challenges and Mechanics (ECM4) - working on small scales
  • Place of Presentation: イギリス（アバディーン）
  • Year and Date: 2015-08-13
  • Invited
• [Presentation] Functional One-Dimensional Coordination Polymers (2015)
  • Author(s): Ryota Sakamoto
  • Organizer: The Third China-Japan Joint Symposium on Inorganic and Nanomaterial Science
  • Place of Presentation: 中国（北京）
  • Year and Date: 2015-06-13
  • Invited
• [Presentation] 金属錯体低次元系のボトムアップ合成と機能発現 (2015)
  • Author(s): 坂本 良太
  • Organizer: 電気学会 新しい原子分子組織化物質・材料創出に向けた光・量子ビーム応用技術調査専門委員会
  • Place of Presentation: 東京理科大学神楽坂キャンパス（東京都新宿区）
  • Invited
• [Presentation] 省エネルギーおよびエネルギー創出を担う「ボトムアップ型」ナノシート (2015)
  • Author(s): 坂本 良太
  • Organizer: 一般財団法人 エヌエフ基金 第4回(2015年度) 研究発表会
  • Place of Presentation: 学士会館（東京都千代田区）
  • Invited
• [Book] 二次元物質の科学 (2017)
  • Author(s): 日本化学会
  • Total Pages: 224
  • Publisher: 化学同人
  • ISBN: 9784759813852