Synthesis and Properties of Functionalized Buckybowls

2013 Fiscal Year Final Research Report

• Project/Area Number: 23350024
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Institute for Molecular Science
• Principal Investigator: SAKURAI Hidehiro 分子科学研究所, 協奏分子システム研究センター, 准教授 (00262147)
• Project Period (FY): 2011-04-01 – 2014-03-31
• Keywords: バッキーボウル / 湾曲π / 電子輸送性 / 立体電子効果

Research Abstract

Synthetic methods for various type of functionalized buckybowls has been developed including C3 symmetric and unsymmetrical sumanenes, C2 symmetric corannulene derivatives, and fluorinated buckybowls.
The thus-prepared functionalized buckybowls exhibit unique properties. In particular, crystals having columnar stacking structure shows high electron mobility even in the case of corannulene derivatives, which does not usually shows the electron mobility.
The first example of the through-bond stereoelectronic effect of curved aromatic compounds was found in buckybowls, benzylic substituted sumanenes. Methyl- and hydroxyl-sumanene favour the endo-R conformer due to the different strength of hyperconjugation of the benzylic C-H bond and the bowl between the endo-R and exo-R conformers.

Research Products

• [Journal Article] Beam-induced graphitic carbon cage transformation from sumanene aggregates (2014)
  • Author(s): J-i. Fujita, M. Tachi, K. Murakami, H. Sakurai, Y. Morita, S. Higashibayashi, M. Takeguchi
  • Journal Title: Appl. Phys. Lett Volume: 104 Pages: 043107. (5)
  • DOI: 10.1063/1.4863739
  • Peer Reviewed
• [Journal Article] Fluorinated and Trifluoromethylated Corannulenes (2013)
  • Author(s): B. M. Schmidt, B. Topolinski, M. Yamada, S. Higashibayashi, M. Shionoya, H. Sakurai, D. Lentz
  • Journal Title: Chem. Eur. J. Volume: 19 Pages: 13872-13880
  • DOI: 10.1002/chem.201301910
  • Peer Reviewed
• [Journal Article] Sumanenylferrocenes and their solid state self-assembly (2013)
  • Author(s): B. Topolinski, B. M. Schmidt, S. Higashibayashi, H. Sakurai, D. Lentz
  • Journal Title: Dalton Trans Volume: 42 Pages: 13809-13812
  • DOI: 10.1039/C3DT51569A
  • Peer Reviewed
• [Journal Article] Stereoelectronic Effect of Curved Aromatic Structure Favouring the Unexpected Endo Conformation of Benzylic Substituted Sumanene (2013)
  • Author(s): S. Higashibayashi, S. Onogi, H. K. Srivastava, G. N. Sastry, Y.-T. Wu, H. Sakurai
  • Journal Title: Angew. Chem. Int. Ed Volume: 52 Pages: 7314-7316
  • DOI: 10.1002/anie.201303134
  • Peer Reviewed
• [Journal Article] Synthesis of Substituted Sumanenes by Aromatic Electrophilic Substitution Reactions (2013)
  • Author(s): B. B. Shrestha, S. Karanjit, G. Panda, S. Higashibayashi, H. Sakurai
  • Journal Title: Chem. Lett Volume: 42 Pages: 386-388
  • DOI: 10.1246/cl.2013.386
  • Peer Reviewed
• [Journal Article] The Synthesis of Hexaflorosumanene and its Congeners (2013)
  • Author(s): B. M. Schmidt, B. Topolinski, S. Higashibayashi, T. Kojima, M. Kawano, D. Lentz, H. Sakurai
  • Journal Title: Chem. Eur. J Volume: 19 Pages: 3282-3286
  • DOI: 10.1002/chem.201204622
  • Peer Reviewed
• [Journal Article] Electonic Properties of Trifluoromethylated Corannulenes (2012)
  • Author(s): B. M. Schmidt, S. Seki, B. Topolinski, K. Ohkubo, S. Fukuzumi, H. Sakurai, D. Lentz
  • Journal Title: Angew. Chem. Int. Ed Volume: 51 Pages: 11385-11388
  • DOI: 10.1002/anie.201205757
  • Peer Reviewed
• [Journal Article] Emission Amplification by Sumanene Nanocrystals in an Onigiri-Type Organic-Organic Assembly (2012)
  • Author(s): Y. Morita, S. Nakao, S. Haesuwannakij, S. Higashibayashi, H. Sakurai
  • Journal Title: Chem. Commun Volume: 48 Pages: 9050-9052
  • DOI: 10.1039/C2CC33643J
  • Peer Reviewed
• [Journal Article] Enantioselective synthesis of a chiral nitrogen-doped buckybowl (2012)
  • Author(s): Q.-T. Tan, S. Higashibayashi, S. Karanjit, H. Sakurai
  • Journal Title: Nat. Commun Volume: 3 Pages: 891
  • DOI: 10.1038/ncomms1896
  • Peer Reviewed
• [Journal Article] Palladium-catalyzed Arylation of Methylene -Bridged Polyarenes : Synthesis and Structures of 9-Arylfluorene Derivatives (2012)
  • Author(s): J.-J. Chen, S. Onogi, Y.-C. Hsieh, C.-C. Hsiao, S. Higashibayashi, H. Sakurai, Y.-T. Wu
  • Journal Title: Adv. Synth. Catal Volume: 354 Pages: 1551-1558
  • DOI: 10.1002/adsc.201100931
  • Peer Reviewed
• [Journal Article] Trimethylsumanene : Enantioselective Synthesis, Substituent Effect on Bowl Structure, Inversion Energy, and Electron Conductivity (2012)
  • Author(s): S. Higashibayashi, R. Tsuruoka, Y. Soujanya, U. Purushotham, G. N. Sastry, S. Seki, T. Ishikawa, S. Toyota, H. Sakurai
  • Journal Title: Bull. Chem. Soc. Jpn Volume: 85 Pages: 450-467
  • DOI: 10.1246/bcsj.20110286
  • Peer Reviewed
• [Journal Article] Selective Synthesis of C3 Symmetric Functionalized Sumanenes (2012)
  • Author(s): S. Higashibayashi, Nasir Baig R. B., Y. Morita, H. Sakurai
  • Journal Title: Chem. Lett Volume: 41 Pages: 84-86
  • DOI: 10.1246/cl.2012.84
  • Peer Reviewed
• [Presentation] バッキーボウルの特徴を生かした機能開発へ向けて (2014)
  • Author(s): 櫻井英博
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学, 名古屋市, 愛知
  • Year and Date: 2014-03-30
  • Invited
• [Presentation] 精密合成法を基盤とした非平面π共役化合物「バッキーボウル」に関する研究 (2014)
  • Author(s): 櫻井英博
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学, 名古屋市, 愛知
  • Year and Date: 2014-03-27
  • Invited
• [Presentation] バッキーボウル化学におけるキラリティ (2014)
  • Author(s): 櫻井英博
  • Organizer: 第5回キラルサイエンス&テクノロジーシンポジウム
  • Place of Presentation: 早稲田大学 ,新宿区, 東京
  • Year and Date: 2014-02-28
  • Invited
• [Presentation] Substituted Sumanenes : From Fundamental to Applied Research (2013)
  • Author(s): H. Sakurai
  • Organizer: 9th IUPAC International Symposium on Novel Materials and their Synthesis and 21th International Symposium on Fine Chemistry and Functional Polymers
  • Place of Presentation: Fudan University, Shanghai, China
  • Year and Date: 2013-10-21
  • Invited
• [Presentation] Synthesis of Sumanene and Related Buckybowls (2013)
  • Author(s): H. Sakurai
  • Organizer: 15th Asian Chemical Congress
  • Place of Presentation: Resort World Sentosa, Singapore
  • Year and Date: 2013-08-20
  • Invited
• [Presentation] Asymmetric Synthesis of C3 Symmetric Buckybowls, PERCH-CIC Congress VIII (2013)
  • Author(s): H. Sakurai
  • Organizer: Jomtien Palm Beach Hotel & Resort
  • Place of Presentation: Pattaya, Thailand
  • Year and Date: 2013-05-06
• [Presentation] お椀型共役化合物「バッキーボウル」の化学 (2012)
  • Author(s): 櫻井英博
  • Organizer: 奈良先端未来開拓コロキウム2012
  • Place of Presentation: 奈良先端科学技術大学院大学, 生駒市, 奈良
  • Year and Date: 20121208-09
  • Invited
• [Presentation] Chemical Synthesis of Nitrogen-doped Buckybowls (2012)
  • Author(s): H. Sakurai, Q.-T. Tan, S. Higashibayashi
  • Organizer: 8th IUPAC International Symposium on Novel Materials and their Synthesis and 21th International Symposium on Fine Chemistry and Functional Polymers
  • Place of Presentation: Xian Jiaotong University, Xian, China
  • Year and Date: 20121014-19
  • Invited
• [Presentation] Enantioselective Synthesis of C3 Symmetric Chiral Triazasumanenes (2011)
  • Author(s): Q.-T. Tan, S. Higashibayashi, S. Karanjit, H. Sakurai
  • Organizer: Catalysis and Fine Chemicals 2011
  • Place of Presentation: 新公会堂, 奈良
  • Year and Date: 20111204-08
• [Presentation] Synthesis of C3 Symmetric Sumanenes (2011)
  • Author(s): S. Higashibayashi, R. Tsuruoka, R. B. Nasir Baig, H. Sakurai
  • Organizer: 14th International Symposium on Novel Aromatic Compounds
  • Place of Presentation: Oregon University, Eugene, Oregon, USA
  • Year and Date: 20110724-29
• [Book] 精密有機合成によるカーボンπ空間の構築,高次π空間の創発と機能開発,赤阪健編 (2013)
  • Author(s): 櫻井英博
  • Total Pages: 40-43
  • Publisher: シーエムシー出版
• [Book] 精密合成が拓くπ電子科学, CSJ カレントレビュー12未来材料を創出するπ電子系の科学-新しい合成・構造・機能化研究,赤阪健,岩澤伸治,山口茂弘,磯部寛之編 (2013)
  • Author(s): 櫻井英博, 東林修平
  • Total Pages: 46-53
  • Publisher: 化学同人
• [Remarks]
  • URL: http://groups.ims.ac.jp/organization/sakurai_g/home.html