Design and synthesis of three dimensionally extended pi-conjugated compounds with heavier group 14 elements

• Project/Area Number: 16K17870
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Tokyo Metropolitan University
• Principal Investigator: Inagaki Yusuke 首都大学東京, 都市環境科学研究科, 助教 (20725626)
• Project Period (FY): 2016-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2018: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000); Fiscal Year 2017: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000); Fiscal Year 2016: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
• Keywords: π電子系化合物 / ケイ素 / π*-σ*共役 / ルイス酸性 / シロキサン結合 / 芳香族性 / ヘテロ五員環 / クロロシラン / 構造有機化学 / ケイ素化学 / 典型元素化学 / 触媒 / 環境調和

Outline of Final Research Achievements

Silyl substituted compounds with extended pi-conjugated system have low lying LUMO by the sigma*-pi* conjugation. In this research cage shaped pi-conjugated compounds with fused Si-O-Si unit were designed and their synthetic route were searched. Molecular modeling by theoretical calculation was used to predict the proper molecular structure and property. Step by step functionalization of heteroaromatic five-membered ring compounds, syntheses of aryl substituted chlorosilanes and their reactivity were investigated.

Academic Significance and Societal Importance of the Research Achievements

機能性分子の設計や化学反応を理解する際に、化学結合（軌道相互作用）についての理解は必要不可欠である。一方で、分子構造の観点から精密に設計された分子であっても、その分子が実際に合成可能かどうかは、反応の条件や合成経路に依存するという制約があり、新たな合成法の開発を通して合成ルートマップを拡張していくことで学術的進歩が生まれると言える。本研究では、自ら設定した化合物の合成を通じて、反応についての考察を深めることができた。

Research Products

• [Journal Article] Ferrocene-diyl Bridged Macrocages: Steric Effects of the Cage on the Redox Properties of Ferrocene Moiety (2018)
  • Author(s): H. Takashima, Y. Inagaki, H. Momma, E. Kwon, K. Yamaguchi, and W. Setaka
  • Journal Title: Organometallics Volume: 37 Issue: 9 Pages: 1501-1506
  • DOI: 10.1021/acs.organomet.8b00154
  • Peer Reviewed
• [Journal Article] Dielectric Relaxation of Powdered Molecular Gyrotops Having a Thiophene Dioxide-diyl as a Dipolar Rotor (2018)
  • Author(s): M. Tsurunaga, Y. Inagaki, H. Momma, E. Kwon, K. Yamaguchi, K. Yoza, W. Setaka
  • Journal Title: Org. Lett. Volume: 20 Issue: 21 Pages: 6934-6937
  • DOI: 10.1021/acs.orglett.8b03087
  • Peer Reviewed
• [Journal Article] A Crystalline Molecular Gyrotop with a Biphenylene Dirotor and its Temperature Dependent Birefringence (2017)
  • Author(s): A. Fujiwara, Y. Inagaki, H. Momma, E. Kwon, K. Yamaguchi, M. Kanno, H. Kono, and W. Setaka
  • Journal Title: Cryst. Eng. Comm. Volume: 19 Issue: 40 Pages: 6049-6056
  • DOI: 10.1039/c7ce01081h
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Molecular Gyrotops with a Five-Membered Heteroaromatic Ring: Synthesis, Temperature-Dependent Orientation of Dipolar Rotors inside the Crystal, and its Birefringence Change (2016)
  • Author(s): T. Masuda, J. Arase, Y. Inagaki, M. Kawahata, K. Yamaguchi, T. Ohhara, A. Nakao, H. Momma, E. Kwon, W. Setaka
  • Journal Title: Cryst. Growth Des. Volume: 16 Issue: 8 Pages: 4392-4401
  • DOI: 10.1021/acs.cgd.6b00508
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Facile Synthesis of a 2,5-Bis(silyl)selenophene-1,1-dioxide and its Photophysical Properties (2016)
  • Author(s): T. Masuda, Y. Inagaki, H. Momma, E. Kwon, W. Setaka
  • Journal Title: New. J. Chem. Volume: 40 Issue: 10 Pages: 8593-8599
  • DOI: 10.1039/c6nj01886f
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] Rotation of the π-System Rotor in Crystalline Molecular Gyrotops (2018)
  • Author(s): Y. Inagaki, K. Yamaguchi, and W. Setaka
  • Organizer: 24th IUPAC Conference on Physical Organic Chemistry (ICPOC24)
  • Int'l Joint Research
• [Remarks] 研究室HP
  • URL: http://wwwchem.apchem.ues.tmu.ac.jp/~setaka/index.php