Chiral arrangement of metal ions and their physical properties

• Project/Area Number: 15K13637
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: The University of Tokyo
• Principal Investigator: NOZAKI kyoko 東京大学, 大学院工学系研究科(工学部), 教授 (60222197)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2016: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2015: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
• Keywords: 有機化学

Outline of Final Research Achievements

We have accomplished the synthesis of metal complexes of [7]-helicene bearing a cyclopentadiene moiety in the middle ring starting from optically active biphenanthrol. The helicene cyclopentadienyl anion was complexed with Ru(II) ion to form a complex consists of one helicene per Ru(II) and one consists of two helicenes per Ru(II). Their chiroptical natures were elucidated both in a solution and in a solid state. In addition, a complex consists of one helicene and two Ru(II) centers was synthesized. This complex exhibited unique phosphorescence emission, which could be attributed to the electron transfer between the two metal centers.

Research Products

• [Journal Article] Synthesis of Optically Pure Helicene Metallocenes (2017)
  • Author(s): M. Akiyama, K. Nozaki
  • Journal Title: Angew. Chem. Int. Ed. Volume: 56 Issue: 8 Pages: 2040-2044
  • DOI: 10.1002/anie.201611488
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis and Properties of [7]Helicene-like Compounds Fused with a Fluorene Unit (2016)
  • Author(s): H. Oyama, M. Akiyama, K. Nakano, M. Naito, K. Nobusawa, K. Nozaki
  • Journal Title: Org. Lett. Volume: 18 Issue: 15 Pages: 3654-3657
  • DOI: 10.1021/acs.orglett.6b01708
  • Peer Reviewed
• [Presentation] [7]ヘリセンを配位子とする金属錯体の合成と光学特性 (2016)
  • Author(s): 秋山 みどり・土屋 佑斗・石井 あゆみ・長谷川 美貴・倉重 佑輝・野崎 京子
  • Organizer: 第6回CSJ化学フェスタ2016
  • Place of Presentation: タワーホール船堀（東京都 江戸川区）
  • Year and Date: 2016-11-14
• [Presentation] Synthesis and Properties of [7]Helicene Metal Complexes. (2016)
  • Author(s): Midori Akiyama, Yuto Tsuchiya, Ayumi Ishii, Miki Hasegawa, Yuki Kurashige, Kyoko Nozaki
  • Organizer: 錯体化学会第66回討論会
  • Place of Presentation: 福岡大学七隈キャンパス（福岡県 福岡市）
  • Year and Date: 2016-09-10
• [Presentation] 4.Synthesis and Properties of Ruthenocene Derivatives with [7]Helicene as Ligands. (2016)
  • Author(s): 秋山 みどり・土屋 佑斗・石井 あゆみ・長谷川美貴・倉重 祐輝・野崎 京子
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学（京都府 京田辺市）
  • Year and Date: 2016-03-24
• [Presentation] 4.Synthesis and optical properties of a bimetallic complex with a [7]helicene ligand. (2015)
  • Author(s): Midori Akiyama, Kyoko Nozaki
  • Organizer: The 2015 International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2015)
  • Place of Presentation: Hawaii Convention Center, Honolulu, Hawaii, USA
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] 13.Synthesis and optical properties of a bimetallic complex with a [7]helicene ligand. (2015)
  • Author(s): Midori Akiyama, Yuto Tsuchiya, Ayumi Ishii, Miki Hasegawa, Yuki Kurashige, Kyoko Nozaki
  • Organizer: The 8th International Forum on Chemistry of Functional Organic Chemicals (IFOC-8; 第8回創造機能化学国際フォーラム)
  • Place of Presentation: 東京大学（東京都 文京区）
  • Year and Date: 2015-11-15
  • Int'l Joint Research
• [Presentation] 21.[7]ヘリセンを配位子とするルテニウム二核錯体の合成と発光特性 (2015)
  • Author(s): 秋山 みどり・土屋 佑斗・石井 あゆみ・長谷川 美貴・倉重 佑輝・内藤 昌信・野崎 京子
  • Organizer: 第27回配位化合物の光化学討論会
  • Place of Presentation: 佐渡インフォメーションセンター(新潟県 佐渡市）
  • Year and Date: 2015-08-07
• [Book] 3.Higher-Order π-Electron Systems Based on Helicene Molecules (2015)
  • Author(s): M. Akiyama, K. Nakano, K. Nozaki
  • Publisher: Springer
• [Remarks]
  • URL: http://park.itc.u-tokyo.ac.jp/nozakilab/publication/index.html
• [Remarks] 野崎研究室HP
  • URL: http://park.itc.u-tokyo.ac.jp/nozakilab/