強電子相関系配位ナノシートの創製

• Project Area: Molecular Architectonics: Orchestration of Single Molecules for Novel Function
• Project/Area Number: 16H00957
• 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: 西原 寛 東京大学, 大学院理学系研究科(理学部), 教授 (70156090)
• Project Period (FY): 2016-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2017: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000); Fiscal Year 2016: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: 配位ナノシート / CONASH / 強電子相関 / 二次元 / 金属錯体 / ナノシート / 界面合成 / 超薄膜 / ナノ材料 / 有機導体 / 表面・界面物性 / 走査プローブ顕微鏡

Outline of Annual Research Achievements

本研究では、申請者がこれまでに開発してきたメタラジチオレン構造からなるπ共役配位ナノシート（CONASH）のように、錯体ユニット間に強い電子・磁気相互作用を有する「強電子相関系CONASH」の新物質群を開拓し、それらの二次元結晶の大面積化を行う。本研究は新しい化学構造の強電子相関系配位ナノシート（CONASH）の合成、構造解析とキャラクタリゼーション、物性解析の各段階からなる。
本年度はヘキサアミノベンゼンとニッケルからなる新しい強電子相関系ナノシートNiDIを、空気酸化法と電解酸化法の２種類の手法により合成した。空気酸化法では結晶性を有するナノシートを得ることができた。また電解酸化法では電解時間により基板上のナノシートの量を制御できることを見出した。NiDIは可逆な酸化還元特性と電気伝導性を示し、電池やキャパシタへの展開が期待できる。
また、トリアミノベンゼントリチオールとニッケルイオンとの反応により、ビス（アミノチオラト）ニッケル錯体骨格を構成単位とする強電子相関系ナノシートNiATを合成した。界面合成法の合成条件を工夫することで単層のNiATを得ることができた。電子線回折およびX線回折実験からNiATが二次元カゴメ構造を有していることを明らかにした。NiATが電気化学的水素発生反応の効果的な触媒として働き、高い耐酸性を示すことを見出した。NiATは化学的な2H+-2e-反応によりビス（イミノチオラト）ニッケル錯体骨格をユニットとするナノシートNiITに可逆的に変換できることを明らかにした。この変換により材料の電気伝導度が１万倍程度変化することを見出した。この大きな伝導度の違いはNiATとNiITのバンド構造の違いに起因する。
以上のように、これまでにないあらたな機能を有する新しい強電子相関系ナノシートを開発することができた。

Research Progress Status

29年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

29年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Oxidation-Promoted Interfacial Synthesis of Redox-Active Bis(diimino)nickel Nanosheet (2018)
  • Author(s): Eunice J H Phua, Kuo-Hui Wu, Keisuke Wada, Tetsuro Kusamoto, Hiroaki Maeda, Jian Cao, Ryota Sakamoto, Hiroyasu Masunaga, Sono Sasaki, Jia-Wei Mei, Wei Jiang, Feng Liu, Hiroshi Nishihara
  • Journal Title: Chemistry Letters Volume: 47 Issue: 2 Pages: 126-129
  • DOI: 10.1246/cl.170928
  • NAID: 130006337769
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Attachment chemistry of aromatic compounds on a Silicon(100) surface (2018)
  • Author(s): Henriksson Anders、Nishiori Daiki、Maeda Hiroaki、Miyachi Mariko、Yamanoi Yoshinori、Nishihara Hiroshi
  • Journal Title: Surface Science Volume: 669 Pages: 140-144
  • DOI: 10.1016/j.susc.2017.11.017
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Aggregation-Induced Emission Enhancement from Disilane-Bridged Donor-Acceptor-Donor Luminogens Based on the Triarylamine Functionality (2018)
  • Author(s): Usuki Tsukasa、Shimada Masaki、Yamanoi Yoshinori、Ohto Tatsuhiko、Tada Hirokazu、Kasai Hidetaka、Nishibori Eiji、Nishihara Hiroshi
  • Journal Title: ACS Appl. Mater. Interfaces Volume: in press Issue: 15 Pages: 12164-12172
  • DOI: 10.1021/acsami.7b14802
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] A Photochemical Hydrogen Evolution System Combining Cyanobacterial Photosystem I and Platinum Nanoparticle-terminated Molecular Wires (2017)
  • Author(s): Miyachi Mariko、Okuzono Kyoko、Nishiori Daiki、Yamanoi Yoshinori、Tomo Tatsuya、Iwai Masako、Allakhverdiev Suleyman I.、Nishihara Hiroshi
  • Journal Title: Chemistry Letters Volume: 46 Issue: 10 Pages: 1479-1481
  • DOI: 10.1246/cl.170576
  • NAID: 130006140067
  • ISSN: 0366-7022, 1348-0715
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Conducting π-Conjugated Bis(iminothiolato)nickel Nanosheet (2017)
  • Author(s): Xinsen Sun, Kuo-Hui Wu, Ryota Sakamoto, Tetsuro Kusamoto, Hiroaki Maeda, Hiroshi Nishihara
  • Journal Title: Chemistry Letters Volume: 46 Issue: 8 Pages: 1072-1075
  • DOI: 10.1246/cl.170382
  • NAID: 130005906987
  • Peer Reviewed
• [Journal Article] Photocurrent generation of reconstituted photosystem II on self-assembled gold film (2017)
  • Author(s): Miyachi, M.; Ikehira, S.; Nishiori, D.; Yamanoi, Y.;* Yamada, M.; Iwai, M.; Tomo, T.; Allakhverdiev, S. I.; Nishihara, H.*
  • Journal Title: Langmuir Volume: 33 Issue: 6 Pages: 1351-1358
  • DOI: 10.1021/acs.langmuir.6b03499
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Access to Chiral Silicon Centers for Application to Circularly Polarized Luminescence Materials (2017)
  • Author(s): Koga Shinya、Ueki Shuhei、Shimada Masaki、Ishii Ryoma、Kurihara Yu、Yamanoi Yoshinori、Yuasa Junpei、Kawai Tsuyoshi、Uchida Taka-aki、Iwamura Munetaka、Nozaki Koichi、Nishihara Hiroshi
  • Journal Title: The Journal of Organic Chemistry Volume: 82 Issue: 12 Pages: 6108-6117
  • DOI: 10.1021/acs.joc.7b00583
  • 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(aminothiolato)nickel nanosheet as a redox switch for conductivity and an electrocatalyst for the hydrogen evolution reaction (2017)
  • Author(s): Sun Xinsen、Wu Kuo-Hui、Sakamoto Ryota、Kusamoto Tetsuro、Maeda Hiroaki、Ni Xiaojuan、Jiang Wei、Liu Feng、Sasaki Sono、Masunaga Hiroyasu、Nishihara Hiroshi
  • Journal Title: Chemical Science Volume: 8 Issue: 12 Pages: 8078-8085
  • DOI: 10.1039/c7sc02688a
  • Peer Reviewed / Open Access / Int'l Joint Research
• [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] Multifunctional Octamethyltetrasila[2.2]cyclophanes: Conformational Variations, Circularly Polarized Luminescence, and Organic Electroluminescence (2017)
  • Author(s): Shimada Masaki、Yamanoi Yoshinori、Ohto Tatsuhiko、Pham Song-Toan、Yamada Ryo、Tada Hirokazu、Omoto Kenichiro、Tashiro Shohei、Shionoya Mitsuhiko、Hattori Mineyuki、Jimura Keiko、Hayashi Shigenobu、Koike Hikaru、Iwamura Munetaka、Nozaki Koichi、Nishihara Hiroshi
  • Journal Title: J. Am. Chem. Soc. Volume: 139 Issue: 32 Pages: 11214-11221
  • DOI: 10.1021/jacs.7b05671
  • Peer Reviewed
• [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
• [Presentation] Coordination Nanosheet (CONASH) -Synthesis, Structure and Functions (2018)
  • Author(s): Hiroshi Nishihara
  • Organizer: MANA International Symposium 2018
  • Int'l Joint Research / Invited
• [Presentation] Functional Coordination Nanosheets (2018)
  • Author(s): Hiroshi Nishihara
  • Organizer: Internation Conference on Low-dimensional Quantum Materials
  • Int'l Joint Research / Invited
• [Presentation] Coordination Nanosheets of Strongly Correlated Electron Systems (2018)
  • Author(s): Hiroshi Nishihara
  • Organizer: 分子アーキテクトニクス 国際ワークショップ 2018
  • Int'l Joint Research
• [Presentation] 固体発光・円偏光発光を示すオクタメチルテトラシラ[2.2]シクロファンの創製 (2017)
  • Author(s): 島田真樹，山野井慶徳，小池ひかる，岩村宗高，野崎浩一，西原寛
  • Organizer: 第21回ケイ素化学シンポジウム
• [Presentation] 触媒機能を示すナノシートの合成 (2017)
  • Author(s): 中島右喬，坂本良太，邨次智，唯美津木，西原寛
  • Organizer: 錯体化学会第67回討論会
• [Presentation] Bis(dipyrrinato)zinc(II) Coordination Copolymers: Enhancement of Photofunctionalities and Observation of Copolymer Structures (2017)
  • Author(s): Ryojun Toyoda，Ryota Sakamoto，Ryota Matsuoka，Mizuho Tsuchiya，Hiroshi Nishihara
  • Organizer: 錯体化学会第67回討論会
• [Presentation] 円偏光発光を示す一次元配位ポリマーの合成及び物性評価 (2017)
  • Author(s): 青木里紗，豊田良順，Julius Kogel，坂本良太，西原寛
  • Organizer: 錯体化学会第67回討論会
• [Presentation] Electrocheimcal Syntheses of Functional Materials and their Applications (2017)
  • Author(s): Keisuke Wada，Jian Cao，Kuo-Hui Wu，Hiroshi Nishihara
  • Organizer: 2017年電気化学秋季大会
• [Presentation] The development of tetrasila[2.2]cyclophane derivatives for solid-state emission, electroluminescence, and circularly polarized luminescence (2017)
  • Author(s): 島田真樹，山野井慶徳，大戸達彦，山田亮，Pham Song-Toan，夛田博一，小池ひかる，岩村宗高，野崎浩一，西原寛
  • Organizer: 2017年光化学討論会
• [Presentation] The development of tetrasila[2.2]cyclophane derivatives for solid-state emission，electroluminescence，and circularly polarized luminescence (2017)
  • Author(s): 島田真樹，山野井慶徳，大戸達彦，山田亮，Pham Song-Toan，夛田博一，小池ひかる，岩村宗高，野崎浩一，西原寛
  • Organizer: 2017年光化学討論会
• [Presentation] Magnetic field effect on luminescence behaviors of organic radicals in rigid matrices (2017)
  • Author(s): Shun Kimura，Tetsuro Kusamto，Shojiro Kimura，Hiroshi Nishihara
  • Organizer: 2017年光化学討論会
• [Presentation] Liquid/liquid Interfacial Synthesis of ''Click'' Nanosheets (2017)
  • Author(s): Ryo Shiotsuki，Amalia Rapakousiou，Ukyo Nakajima，Ryota Sakamoto，Hiroshi Nishihara
  • Organizer: 1st European Conference on Chemistry of Two-Dimensional Materials
  • Int'l Joint Research
• [Presentation] ynthesis and physical properties of tetrasila[2.2]thiophenophane derivatives for the luminescent and chiroptical materials (2017)
  • Author(s): Masaki Shimada，Yoshinori Yamanoi，Kenichiro Omoto，Shohei Tashiro，Mitsuhiko Shionoya，Tatsuhiko Ohto，Song-Toan Pham，Ryo Yamada，Hirokazu Tada，Mineyuki Hattori，Keiko Jimura，Shigenobu Hayashi，Hikaru Koike，Munetaka Iwamura，Koichi Nozaki，Hiroshi Nishihara
  • Organizer: 254th ACS National Meeting & Exposition
  • Int'l Joint Research
• [Presentation] Photofunctionality Enhancement of Coordination Nanowires Based on Bis(dipyrrinato)zinc(II) Complexes (2017)
  • Author(s): Ryojun Toyoda，Ryota Sakamoto，Ryota Matsuoka，Mizuho Tsuchiya，Hiroshi Nishihara
  • Organizer: 6th Asian Conference on Coordination Chemistry (ACCC6)
  • Int'l Joint Research
• [Presentation] A possible quantum spin liquid state on highly anisotropic triangular lattices of bilayer Mott system (2017)
  • Author(s): Tetsuro Kusamoto，Chie Ohde，Shiori Sugiura，Taichi Terashima，Shinya Uji，Satoshi Yamashita，Yasuhiro Nakazawa，Hiroshi Nishihara
  • Organizer: The 12th International Symposium on Crystalline Organic Metals, Superconductors and Magnets (ISCOM2017)
  • Int'l Joint Research
• [Presentation] A chiral one-dimensional coordination polymer showing circularly polarized luminescence (2017)
  • Author(s): Risa Aoki，Ryojun Toyoda，Julius Kogel，Ryota Matsuoka，Ryota Sakamoto，Hiroshi Nishihara
  • Organizer: 6th Asian Conference on Coordination Chemistry (ACCC6)
  • Int'l Joint Research
• [Presentation] A luminescent triarylmethyl radical with two pyridyl groups: Superior photostability and the formation of 1D CuII coordination polymer (2017)
  • Author(s): Shun Kimura，Tetsuro Kusamoto，Hiroshi Nishihara
  • Organizer: The 6th Asian Conference on Coordination Chemistry (ACCC6)
  • Int'l Joint Research
• [Presentation] A Photostable Luminescent Triarylmethyl Radical with Two Pyridyl Groups (2017)
  • Author(s): Shun Kimura，Tetsuro Kusamoto，Hiroshi Nishihara
  • Organizer: 8th Pacific Symposium on Radical Chemistry (PSRC-8)
  • Int'l Joint Research
• [Presentation] Synthesis, structure and functions of coordination nanosheet (CONASH) (2017)
  • Author(s): Hiroshi Nishihara
  • Organizer: Molecular Electronics and Bioelectronics
  • Int'l Joint Research / Invited
• [Presentation] Coordination nanosheet (CONASH) Synthesis, structure and functions (2017)
  • Author(s): Hiroshi Nishihara
  • Organizer: 6th Asian Conference on Coordination Chemistry (ACCC6)
  • Int'l Joint Research / Invited
• [Presentation] Coordination Nanosheets -Synthesis, Structure and Funtions (2017)
  • Author(s): Hiroshi Nishihara
  • Organizer: 11th Japan-China Joint Symposium on Metal Cluster Compounds
  • Int'l Joint Research / Invited
• [Presentation] Electronic properties and charge transport of coordination nanosheet (CONASH) (2017)
  • Author(s): Naoya Fukui，Kazuo Nakazato，Sono Sasaki，Hiroshi Nishihara
  • Organizer: WINDS17
  • Int'l Joint Research / Invited
• [Presentation] Functional Coordination Nanosheets (2017)
  • Author(s): Hiroshi Nishihara
  • Organizer: The 4th Japan-Canada Joint Symposium on Coordination Chemistry
  • Int'l Joint Research / Invited
• [Presentation] 強電子相関系配位ナノシートの創製 (2017)
  • Author(s): 西原 寛
  • Organizer: 新学術領域研究「分子アーキテクトニクス：単一分子の組織化と新機能創成」第8回領域会議
• [Presentation] 強電子相関系配位ナノシートの創製 (2017)
  • Author(s): 前田 啓明，西原 寛
  • Organizer: 新学術領域研究「分子アーキテクトニクス：単一分子の組織化と新機能創成」第9回領域会議
• [Presentation] アニオン交換によるビス（テルピリジン）金属錯体ナノシートの電気伝導度向上 (2017)
  • Author(s): 五百川 惟志，前田 啓明，Soan Toan Pham，夛田 博一，西原 寛
  • Organizer: 新学術領域研究「分子アーキテクトニクス：単一分子の組織化と新機能創成」第8回研究会
• [Presentation] 低次元配位ネットワークの界面合成と物理・化学機能 (2017)
  • Author(s): 西原寛
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶応義塾大学日吉キャンパス（神奈川県横浜市）
  • Invited
• [Presentation] 配位プログラミングと界面 (2017)
  • Author(s): 西原寛
  • Organizer: 分子研研究会「金属錯体の情報制御と機能連動」
  • Place of Presentation: 分子科学研究所（愛知県岡崎市）
  • Invited
• [Presentation] Coordination Nanosheet (CONASH) - Synthesis, Structure and Functions (2017)
  • Author(s): Hiroshi Nishihara
  • Organizer: NTU-SNU-UTokyo Chemistry Symposium
  • Place of Presentation: 東京大学本郷キャンパス（東京都文京区）
  • Int'l Joint Research / Invited
• [Presentation] 液相界面を駆使したグラフィジインナノシートの合成 (2016)
  • Author(s): 松岡亮太, 坂本良太, 西原寛
  • Organizer: 第65回高分子討論会
  • Place of Presentation: 神奈川大学横浜キャンパス（神奈川県横浜市）
• [Presentation] Electron Transport Behavior Analysis of Bis(terpyridine)metal Complex Wires on Electrodes (2016)
  • Author(s): Hiroaki Maeda, Ryota Sakamoto, Hiroshi Nishihara
  • Organizer: PRiME2016
  • Place of Presentation: Honolulu, Hawaii, United States
  • Int'l Joint Research
• [Presentation] Coordination Nanosheet (CONASH) - Synthesis, Structure and Functions (2016)
  • Author(s): Hiroshi Nishihara
  • Organizer: UK-Japan Workshop on Chemistry, Physics, and Applications of Coordination Nanosheets
  • Place of Presentation: Cambridge, UK
  • Int'l Joint Research / Invited
• [Presentation] Interfacial Coordination Programming of 1D and 2D Materials (2016)
  • Author(s): Hiroshi Nishihara
  • Organizer: NIMS Seminar
  • Place of Presentation: 物質・材料研究機構（茨城県つくば市）
  • Int'l Joint Research / Invited
• [Presentation] Coordination Nanosheet (CONASH) - Synthesis, Structure and Functions (2016)
  • Author(s): Hiroshi Nishihara
  • Organizer: IWPCC2016
  • Place of Presentation: Altay, Russia
  • Int'l Joint Research / Invited
• [Presentation] Interfacial Coordination Programming of 1D and 2D Molecular Networks (2016)
  • Author(s): Hiroshi Nishihara
  • Organizer: The 3rd Japan-Taiwan-Singapore-Hong Kong Quadrilateral Symposium on Coordination Chemistry
  • Place of Presentation: Academia Sinica, Taiwan
  • Int'l Joint Research / Invited
• [Presentation] Interfacial Coordination Programming of 1D and 2D Material (2016)
  • Author(s): Hiroshi Nishihara
  • Organizer: ICCC2016
  • Place of Presentation: Brest, France
  • Int'l Joint Research / Invited
• [Presentation] Photo- and Electro-functional Molecular Systems Based on Coordination Programming (2016)
  • Author(s): Hiroshi Nishihara
  • Organizer: Department Seminar, KIT
  • Place of Presentation: Karlsruhe, Germany
  • Int'l Joint Research / Invited
• [Presentation] Coordination Nanosheets - Synthesis, Structure and Functions (2016)
  • Author(s): Hiroshi Nishihara
  • Organizer: S2DP-2
  • Place of Presentation: 東大寺総合文化センター（奈良県奈良市）
  • Int'l Joint Research / Invited