円筒型配位子の配位プログラミングによる新規な物質移動および制御システムの開発

• Project Area: Coordination Programming - Science of Molecular Superstructures for Chemical Devices
• Project/Area Number: 24108707
• 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: Kanazawa University (2013); University of Tsukuba (2012)
• Principal Investigator: 秋根 茂久 金沢大学, 物質化学系, 教授 (30323265)
• Project Period (FY): 2012-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥8,320,000 (Direct Cost: ¥6,400,000、Indirect Cost: ¥1,920,000); Fiscal Year 2013: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2012: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
• Keywords: ナノチューブ / 分子認識 / 大環状化合物 / 自己集合 / 超分子錯体 / チューブ型金属錯体

Research Abstract

本研究では、新規なハイブリッド型金属錯体ナノチューブの構成要素となり得る円筒型化合物とその関連化合物の構築を目指した研究を行った。構成要素としてペンタセンキノンを用いた系では、クラウンエーテルとアルカリ金属イオンとの錯形成を利用した大環状自己集合錯体の構築を行った。ペンタセンキノンに二つの15-クラウン-5部位を導入した分子を合成し、これとカリウムイオン、ルビジウムイオン、セシウムイオンを錯形成させたところ、大環状の2:2型錯体が定量的に生成した。すなわち、扁平なチューブの構成要素となる大環状構造を簡単な手法で効率的に得ることに成功した。さらに、チューブの三つ又分岐部に相当する構造の構成要素となり得るカゴ型メタロホスト分子の合成を行い、その特異なゲスト認識能を明らかにした。

Current Status of Research Progress

Reason

25年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

25年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Perfect encapsulation of guanidinium ion in a helical trinickel(II) metallocryptand for efficient regulation of helix inversion rate (2014)
  • Author(s): Akine, S.; Miyashita, M.; Piao, S.; Nabeshima, T.
  • Journal Title: Inorg. Chem. Front. Volume: 1 Issue: 1 Pages: 53-57
  • DOI: 10.1039/c3qi00067b
  • Peer Reviewed
• [Journal Article] Dynamic helicity control of single-helical oligooxime metal complexes by coordination of chiral carboxylate ions (2014)
  • Author(s): Sairenji, S.; Akine, S.; Nabeshima, T.
  • Journal Title: Tetrahedron Lett. Volume: 55 Issue: 12 Pages: 1987-1990
  • DOI: 10.1016/j.tetlet.2014.02.009
  • Peer Reviewed
• [Journal Article] Dynamic Helicity Control of a Single-Helical Oligooxime Complex and Acid-Base Triggered Repeated Helicity Inversion Mediated by Amino Acids (2014)
  • Author(s): Sairenji, S.; Akine, S.; Nabeshima, T.
  • Journal Title: Chem. Lett. Volume: 印刷中 Issue: 7 Pages: 1107-1109
  • DOI: 10.1246/cl.140263
  • NAID: 130004868263
  • Peer Reviewed / Open Access
• [Journal Article] Programmed multiple complexation for the creation of helical structures from acyclic phenol-bipyridine oligomer ligands (2013)
  • Author(s): Akine, S.; Nagumo, H.; Nabeshima, T.
  • Journal Title: Dalton Trans. Volume: 42 Issue: 45 Pages: 15974-15986
  • DOI: 10.1039/c3dt51240a
  • Peer Reviewed
• [Journal Article] Stepwise Helicity Inversions by Multisequential Metal Exchange (2013)
  • Author(s): Akine, S.; Sairenji, S.; Taniguchi, T.; Nabeshima, T.
  • Journal Title: J. Am. Chem. Soc. Volume: 135 Issue: 35 Pages: 12948-12951
  • DOI: 10.1021/ja405979v
  • Peer Reviewed
• [Journal Article] Synthesis of Planar Metal Complexes and the Stacking Abilities of Naphthalenediol-Based Acyclic and Macrocyclic Salen-Type Ligands (2013)
  • Author(s): Akine, S.; Varadi, Z.; Nabeshima, T.
  • Journal Title: Eur. J. Inorg. Chem. Volume: 2013 Issue: 35 Pages: 5987-5998
  • DOI: 10.1002/ejic.201300917
  • Peer Reviewed
• [Journal Article] Cage-like tris(salen)-type metallocryptand for cooperative guest recognition (2013)
  • Author(s): Akine, S.; Piao, S.; Miyashita, M.; Nabeshima, T.
  • Journal Title: Tetrahedron Lett. Volume: 54 Issue: 48 Pages: 6541-6544
  • DOI: 10.1016/j.tetlet.2013.09.098
  • Peer Reviewed
• [Journal Article] Conformational control of electron-rich calix[6]arene skeleton by paraquat recognition (2013)
  • Author(s): Akine, S.; Kusama, D.; Nabeshima, T
  • Journal Title: Tetrahedron Lett Volume: 54 Issue: 3 Pages: 205-209
  • DOI: 10.1016/j.tetlet.2012.10.105
  • Peer Reviewed
• [Journal Article] Ligand Modification of Cyclometalated Ruthenium Complexes in the Aerobic Oxidative Dehydrogenation of Imidazolines (2013)
  • Author(s): Aiki, S.; Kijima, Y.; Kuwabara, J.; Taketoshi, A.; Koizumi, T.; Akine, S.; Kanbara, T
  • Journal Title: ACS Catal Volume: 3 Issue: 5 Pages: 812-816
  • DOI: 10.1021/cs300811w
  • Peer Reviewed
• [Journal Article] Hierarchical Helix of Helix in the Crystal: Formation of Variable-Pitch Helical π-Stacked Array of Single-Helical Dinuclear Metal Complexes (2012)
  • Author(s): Akine, S.; Nagumo, H.; Nabeshima, T
  • Journal Title: Inorg. Chem Volume: 51 Issue: 10 Pages: 5506-5508
  • DOI: 10.1021/ic3004273
  • Peer Reviewed
• [Journal Article] Design and controlled emission properties of bioorganometallic compounds composed of uracils and organoplatinum(II) moieties (2012)
  • Author(s): Moriuchi, T.; Sakamoto, Y.; Noguchi, S.; Fujiwara, T.; Akine, S.; Nabeshima, T.; Hirao, T
  • Journal Title: Dalton Trans Volume: 41 Issue: 28 Pages: 8524-8531
  • DOI: 10.1039/c2dt30533j
  • Peer Reviewed
• [Journal Article] Oligometallic Template Strategy for Synthesis of a Macrocyclic Dimer-Type Octaoxime Ligand for Its Cooperative Complexation (2012)
  • Author(s): Akine, S.; Tadokoro, T.; Nabeshima, T
  • Journal Title: Inorg. Chem Volume: 51 Issue: 21 Pages: 11478-11486
  • DOI: 10.1021/ic3012525
  • Peer Reviewed
• [Presentation] 開口部に架橋ジアミン配位子をもつ新規かご型コバルト三核錯体の合成とゲスト認識 (2014)
  • Author(s): 宮下真人・秋根茂久・鍋島達弥
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋
• [Presentation] アルカリ金属イオンとの錯形成を利用したペンタセンキノン二量体の形成 (2014)
  • Author(s): 高槻百合・秋根茂久・鍋島達弥
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋
• [Presentation] シリル基の除去反応を活用したらせん型亜鉛多核錯体の動的ヘリシティー反転 (2014)
  • Author(s): 西連地志穂・秋根茂久・鍋島達弥
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋
• [Presentation] Formation of Pentacenequinone Dimer by Sandwich Complexation with Alkali Metal Ion (2014)
  • Author(s): Yuri Takatsuki, Shigehisa Akine, Tatsuya Nabeshima
  • Organizer: CENIDE-CNMM-TIMS Joint Symposium on Interdisciplinary Nano-Science and Technology
  • Place of Presentation: Hsinchu, Taiwan
• [Presentation] Multi-step Helicity Inversion of Helical Multinuclear Complex by Stepwise Metal Exchange (2014)
  • Author(s): Shigehisa Akine, Shiho Sairenji, Tatsuya Nabeshima
  • Organizer: International Symposium on Coordination Programming (ISCP2014)
  • Place of Presentation: Tokyo, Japan
• [Presentation] らせん構造をもつクリプタンド型Trisalophメタロホストの合成とゲスト認識 (2013)
  • Author(s): 宮下真人、秋根茂久、鍋島達弥
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学，草津市
  • Year and Date: 2013-03-22
• [Presentation] 化学変換を活用したらせん型ヘキサオキシム多核錯体の動的ヘリシティー制御 (2013)
  • Author(s): 西連地志穂、秋根茂久、鍋島達弥
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学，草津市
  • Year and Date: 2013-03-22
• [Presentation] らせん型多核錯体の合成・機能と動的ヘリシティー制御 (2013)
  • Author(s): 秋根茂久
  • Organizer: 第13回リング・チューブ超分子研究会
  • Place of Presentation: 東京工業大学，横浜市
  • Year and Date: 2013-02-22
  • Invited
• [Presentation] キラルカウンターイオンの化学変換によるらせん型錯体の動的ヘリシティー制御 (2013)
  • Author(s): 西連地志穂・秋根茂久・鍋島達弥
  • Organizer: 第10回ホスト・ゲスト化学シンポジウム
  • Place of Presentation: 和歌山
• [Presentation] 三つの遷移金属錯体部位をもつメタロクリプタンドの合成と分子認識 (2013)
  • Author(s): 宮下真人・秋根茂久・鍋島達弥
  • Organizer: 第10回ホスト・ゲスト化学シンポジウム
  • Place of Presentation: 和歌山
• [Presentation] キラルなカルボン酸イオンの化学変換を活用したらせん型メタロフォルダマーの動的ヘリシティー制御 (2013)
  • Author(s): 西連地志穂・秋根茂久・鍋島達弥
  • Organizer: 第24回基礎有機化学討論会
  • Place of Presentation: 東京
• [Presentation] 三つのsaloph部位を有するニッケル三核メタロクリプタンドの合成とゲスト認識 (2013)
  • Author(s): 宮下真人・秋根茂久・鍋島達弥
  • Organizer: 第3回CSJ化学フェスタ
  • Place of Presentation: 東京
• [Presentation] 複数のフェニル基を導入したビピリジンおよびテルピリジン配位子の合成と錯形成 (2013)
  • Author(s): 小林 愛・秋根茂久・鍋島達弥
  • Organizer: 第3回CSJ化学フェスタ
  • Place of Presentation: 東京
• [Presentation] クラウンエーテル部位を導入したペンタセンキノンの合成と錯形成 (2013)
  • Author(s): 高槻百合・秋根茂久・鍋島達弥
  • Organizer: 第3回CSJ化学フェスタ
  • Place of Presentation: 東京
• [Presentation] らせん構造をもつニッケル三核メタロクリプタンドの合成と分子認識 (2013)
  • Author(s): 宮下真人・秋根茂久・鍋島達弥
  • Organizer: 錯体化学会第63回討論会
  • Place of Presentation: 西原
• [Presentation] Stepwise Helicity Inversion of Helical Complex by Exchange of Constituent Metal Ions (2013)
  • Author(s): Shiho Sairenji, Shigehisa Akine, Tatsuya Nabeshima
  • Organizer: The 3rd German-Japan Nanoworkshop ~ Energy Conversion and Storage ~
  • Place of Presentation: Tsukuba, Japan
• [Presentation] Multi-step helicity inversion of helical oligooxime complex by exchange of constituent metal ions (2013)
  • Author(s): Shiho Sairenji, Shigehisa Akine, Tatsuya Nabeshima
  • Organizer: 4th Tetrahedron Symposium-Asian Edition
  • Place of Presentation: Seoul, Korea
• [Presentation] Development of a rational strategy for helicity inversion of helical metal complexes (2013)
  • Author(s): Shigehisa Akine, Tatsuya Nabeshima
  • Organizer: 4th Asian Conference on Coordination Chemistry
  • Place of Presentation: Jeju, Korea
• [Presentation] Multi-step Helicity Inversion of Helical Metallofoldamers by Metal Exchange (2012)
  • Author(s): Shiho Sairenji, Shigehisa Akine, Tatsuya Nabeshima
  • Organizer: 3rd International Symposium on Creation of Functional Materials
  • Place of Presentation: University of Tsukuba, Tsukuba, Japan
  • Year and Date: 2012-12-10
• [Presentation] Synthesis of Cage-like Trisaloph Metallohost and Guest Recognition (2012)
  • Author(s): Masato Miyashita, Shigehisa Akine, Tatsuya Nabeshima
  • Organizer: 3rd International Symposium on Creation of Functional Materials
  • Place of Presentation: University of Tsukuba, Tsukuba, Japan
  • Year and Date: 2012-12-10
• [Presentation] Helicity Control of Helical Metal Complexes by Molecular Leverage Mechanism (2012)
  • Author(s): Shigehisa Akine, Tatsuya Nabeshima
  • Organizer: The Twelfth International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-12)
  • Place of Presentation: Rihga Royal Hotel Kyoto, Kyoto, Japan
  • Year and Date: 2012-11-12
• [Presentation] Controlling helical handedness of dynamic single-helical metal complexes (2012)
  • Author(s): Shigehisa Akine
  • Organizer: Japan-India Bilateral Seminar on Supramolecular Nanomaterials for Energy Innovation
  • Place of Presentation: Alpha Anabuki Hall, Takamatsu, Japan
  • Year and Date: 2012-10-15
  • Invited
• [Presentation] Strategic Helicity Control of Single-Helical Metal Complexes (2012)
  • Author(s): 秋根茂久
  • Organizer: 錯体化学会第62回討論会ミニシンポジウム“Supramolecular Systems for Materials Science by Coordination Chemistry”
  • Place of Presentation: 富山大学，富山市
  • Year and Date: 2012-09-21
  • Invited
• [Presentation] らせん型ヘキサオキシム金属錯体を利用したヘリシティー制御・反転システム (2012)
  • Author(s): 西連地志穂、秋根茂久、鍋島達弥
  • Organizer: 錯体化学会第62回討論会
  • Place of Presentation: 富山大学，富山市
  • Year and Date: 2012-09-21
• [Presentation] かご型trisalophメタロホストの合成とゲスト認識 (2012)
  • Author(s): 宮下真人、秋根茂久、鍋島達弥
  • Organizer: 第23回基礎有機化学討論会
  • Place of Presentation: 京都テルサ，京都市
  • Year and Date: 2012-09-19
• [Presentation] Strategic Helicity Control of Helical Metal Complexes by Molecular Leverage (2012)
  • Author(s): Shigehisa Akine, Sayaka Hotate, Tatsuya Nabeshima
  • Organizer: The 40th International Conference on Coordination Chemistry (ICCC40)
  • Place of Presentation: Valencia, Spain
  • Year and Date: 2012-09-09
• [Presentation] ジアンモニウム認識を駆動力とするらせん型錯体のヘリシティー制御 (2012)
  • Author(s): 秋根茂久、保立さやか、鍋島達弥
  • Organizer: 第9回ホスト・ゲスト化学シンポジウム
  • Place of Presentation: 北海道大学，札幌市
  • Year and Date: 2012-05-26
• [Presentation] ヘキサ-peri-ヘキサベンゾコロネン骨格をもつ大環状ホスト分子による芳香族化合物の認識 (2012)
  • Author(s): 小沼孝大、秋根茂久、鍋島達弥
  • Organizer: 第9回ホスト・ゲスト化学シンポジウム
  • Place of Presentation: 北海道大学，札幌市
  • Year and Date: 2012-05-26
• [Presentation] Dynamic and Strategic Control of Helical Handedness of Helical Metal Complexes (2012)
  • Author(s): Shigehisa Akine
  • Organizer: The 3rd Tsukuba International Mini-symposium on Hybridization between Main Group Element Chemistry and π -Electron Chemistry
  • Place of Presentation: University of Tsukuba, Tsukuba, Japan
  • Year and Date: 2012-05-18
  • Invited