Construction of curved molecules based on the unique pi-polarization of azulene

• Project/Area Number: 16K05697
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Yamaguchi University
• Principal Investigator: Toshihiro Murafuji 山口大学, 大学院創成科学研究科, 教授 (40253140)
• Project Period (FY): 2016-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2018: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2017: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2016: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: アズレン / 曲面分子 / 典型元素 / ボリン酸 / 光機能性 / 曲面

Outline of Final Research Achievements

We developed the synthetic method for constructing curved molecules containing azulene units and studied their molecular structures and properties. We found that diazulenylborinic acid ester is a stable and useful synthetic intermediate for constructing the curved molecules. This compound undergoes coupling reactions in the presence of transition metal reagents to form the conjugated cyclized product. The change in the conjugated electronic system clearly appeared in the color change of the product. Furthermore, we established a convenient synthetic route to 2-iodoazulenes. This method made it possible to introduce a 2-azulenyl unit into the metal center.

Academic Significance and Societal Importance of the Research Achievements

本研究は、アズレンに機能発現の鍵となる種々の典型元素を共役させ、各元素の特性を活かしてその特異なπ分極を自在に変えることで、新しい化学性・物理性と機能性を狙っている。「典型元素」と「非ベンゼノイド」という広範囲にわたってこれまで個別に発展を遂げて来た各系の特色を際立たせた「新たな複合電子系」が創出される可能性を持ち、新規な機能性物質の創製に寄与すると期待される。構成単位を求めながら電子系を創出する見知からすれば、国内外を問わず、稀で独創的研究である。

Research Products

• [Journal Article] One-pot synthesis of hypervalent diaryl(iodo)bismuthanes from o-carbonyl iodoarenes by zincation (2019)
  • Author(s): T. Murafuji, A. F. M. Hafizur Rahman, D. Magarifuchi, M. Narita, I. Miyakawa, K. Ishiguro, S. Kamijo
  • Journal Title: Heteroatom Chemistry Volume: 2019 Pages: 1-7
  • DOI: 10.1155/2019/2385064
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis of 2-Iodoazulenes by the Iododeboronation of Azulen-2-ylboronic Acid Pinacol Esters with Copper(I) Iodide (2018)
  • Author(s): M. Narita, T. Murafuji, S. Yamashita, M. Fujinaga, K. Hiyama, Y. Oka, F. Tani, S. Kamijo, K. Ishiguro
  • Journal Title: The Journal of Organic Chemistry Volume: 83 Pages: 1298-1303
  • Peer Reviewed
• [Journal Article] Synthesis and structural characterization of diazulenylborinic acid (2017)
  • Author(s): T. Murafuji, K. Shintaku, K. Nagao, Y. Mikata, K. Ishiguro, S. Kamijo
  • Journal Title: Heterocycles Volume: 94 Issue: 4 Pages: 676-690
  • DOI: 10.3987/com-17-13651
  • NAID: 40021195729
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] ジアズレニルボリン酸から誘導されるお椀型分子の合成検討 (2018)
  • Author(s): 永尾航平、真宅晃平、村藤俊宏、谷 文都、三方裕司、上條 真、石黒勝也
  • Organizer: 第48回複素環化学討論会
• [Presentation] アズレニルジメシチルボランの構造と光吸収および錯形成反応 (2017)
  • Author(s): 成田昌弘、村藤俊宏、上條 真、石黒勝也、三方裕司、谷 文都、俣野善博
  • Organizer: 第44回有機典型元素化学討論会
• [Presentation] アズレン骨格へのジメシチルボリル基の導入と錯形成 (2016)
  • Author(s): 成田昌弘、村藤俊宏、上條 真、石黒勝也、三方裕司、谷 文都、俣野善博
  • Organizer: 第４３回有機典型元素化学討論会
  • Place of Presentation: 仙台市民会館（宮城県仙台市）
  • Year and Date: 2016-12-08