「ボトムアップ型」金属錯体ナノシートの原子層科学

• Project Area: Science of Atomic Layer Systems
• Project/Area Number: 26107510
• 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): 2014-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥7,150,000 (Direct Cost: ¥5,500,000、Indirect Cost: ¥1,650,000); Fiscal Year 2015: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2014: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
• Keywords: ナノシート / 原子層 / 金属錯体

Outline of Annual Research Achievements

「ナノシート」とは究極的な厚みが単原子層に達する二次元高分子を指す。グラフェンなど層状化合物を母体とする「トップダウン型」ナノシートが新しいナノ材料として注目を集めている。一方で有機分子・金属イオンなどからナノシートを直接紡ぎ上げる「ボトムアップ型」ナノシートがここ10年間で勃興してきたが、現状では二次元構造の構築に留まりナノ材料としての有用性を示した例は存在しない。本年度は半導体材料などへの応用が期待される、ジチオレン金属錯体ナノシートのバリエーションの拡張を行った。ニッケルイオンをより重元素のパラジウムに置き換えたナノシートの合成を行い、ペレット化したサンプルについて2.8x10^-2 S/cmという導電性の値を得た。また硫黄を他元素へと置換したナノシートの構築にも取り組んだ。一方、金属錯体ナノシートのもう一つの構成要素である、有機配位子の構造を根本的に見直したナノシートの構築にも取り組んだ。その結果、光電変換機能、光ホスト機能などを見出した。今年度の成果には間に合わなかったが、後半の公募班員として参画できれば、これらの成果が花開くと期待される。なお、これらの新ナノシートの研究に関しては、領域内共同研究として行った。また一部は国際共同研究でもある。新規材料としての「ナノシート」開発が文科省の平成26年度戦略目標に設定されるなど、ナノシートの重要性・注目度は近年飛躍的に増大している。魅力的な物性を有し, ナノ材料として機能する「ボトムアップ型」ナノシートを提案できれば学術界のみならず産業界から注目を集めることは想像に難くない。

Research Progress Status

27年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

27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(中国)
• [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] 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] 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] 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
• [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] Modulation of Electronic State of π-Conjugated Nickelladithiolene Complex Nanosheet (2015)
  • Author(s): Tetsuya Kambe, Tetsuro Kusamoto, Ryota Sakamoto, Hiroshi Nishihara
  • Journal Title: Macromol. Symp. Volume: 351 Issue: 1 Pages: 78-80
  • DOI: 10.1002/masy.201300127
  • Peer Reviewed / Acknowledgement Compliant
• [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] 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] 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] 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
• [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] 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）
  • Int'l Joint Research / 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
  • Int'l Joint Research / 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
  • Int'l Joint Research / 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
  • Int'l Joint Research / 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
  • Int'l Joint Research / 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
  • Int'l Joint Research / 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
  • Int'l Joint Research / 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
  • Int'l Joint Research / 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