Creation and Function of Novel Open-Shell π-Conjugated Systemswith a Weak π-Bond

• Project/Area Number: 23750040
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Kyoto University
• Principal Investigator: SHIMIZU Akihiro 京都大学, 大学院・工学研究科, 助教 (30584263)
• Project Period (FY): 2011 – 2012
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2012: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000); Fiscal Year 2011: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
• Keywords: π 共役系ラジカル / 一重項ビラジカル / キノジメタン / インデノフルオレン / 近赤外吸収 / π共役系 / ラジカル / 一重項テトララジカル / シクロブタジエン / ビラジカル / π電子系

Research Abstract

An indeno[2,1-b]fluorene derivative, a 20π electron hydrocarbon, was synthesized to clarify novel properties associated with singlet diradical characters. The moderate amplitude diradical character of the indeno[2,1-b]fluorene derivative was theoretically and experimentally proved. The indeno[2,1-b]fluorene derivative exhibits an extremely low-energy light absorption band whose absorption end extends to 2000 nm despite its small conjugation space consisting of only 20 π electrons. The present knowledge is useful for the design of new classes of materials based on small molecules with low-energy light absorption.

Research Products

• [Journal Article] Oxidative Cyclodimerization that Follows Tandem Cyclization of Dehydro[14]annulenes Induced by Alkyllithium (2013)
  • Author(s): Shunpei Nobusue, Akihiro Shimizu, Kenji Hori, Ichiro Hisaki, Mikiji Miyata, Yoshito Tobe
  • Journal Title: Angew. Chem. Int. Ed Volume: 52 Issue: 15 Pages: 4184-4188
  • DOI: 10.1002/anie.201210233
  • Peer Reviewed
• [Journal Article] Electrochemical C-H Amination : Synthesis of Aromatic Primary Amines via N-Arylpyridinium Ions (2013)
  • Author(s): 諸藤達也・清水章弘・吉田潤一
  • Journal Title: Journal of American Chemical Society Volume: 135 Issue: 13 Pages: 5000-5003
  • DOI: 10.1021/ja402083e
  • Peer Reviewed
• [Journal Article] Indeno[2,1-b]fluorene: A 20 pi electron hydrocarbon with extremely low energy light absorption (2013)
  • Author(s): A. Shimizu, R. Kishi, M. Nakano, D. Shiomi, K. Sato, T. Takui, I. Hisaki, M. Miyata, and Y. Tobe
  • Journal Title: Angew. Chem. Int. Ed. Volume: 52 Issue: 23 Pages: 6076-6079
  • DOI: 10.1002/anie.201302091
  • Peer Reviewed
• [Journal Article] Theoretical Consideration of Singlet Open-Shell Character of Polyperiacenes Using Clar’s Aromatic Sextet Valence Bond Model and Quantum Chemical Calculations (2012)
  • Author(s): Akihiro Shimizu
  • Journal Title: AIP Conf. Proc. Volume: 1504 Pages: 399-405
  • DOI: 10.1063/1.4771733
  • Peer Reviewed
• [Journal Article] Theoretical Aspects on the Evaluation and Interpretation of the Third-Order Nonlinear Optical Properties of Diradical Compounds (2012)
  • Author(s): Benoit Champagne
  • Journal Title: AIP Conf. Proc. Volume: 1504 Pages: 844-847
  • DOI: 10.1063/1.4771826
  • Peer Reviewed
• [Journal Article] Singlet Open-Shell Character of Conjugated Kekulé Molecules (2012)
  • Author(s): Takashi Kubo
  • Journal Title: AIP Conf. Proc. Volume: 1504 Pages: 883-886
  • DOI: 10.1063/1.4771836
  • Peer Reviewed
• [Journal Article] Aromaticity and π-bond covalency: prominent intermolecular covalent bonding interaction of a Kekule hydrocarbon with very significant singlet biradical character (2012)
  • Author(s): Shimizu, A.; Hirao, Y.; Matsumoto, K.; Kurata, H.; Kubo, T.; Uruichi M.; Yakushi, K
  • Journal Title: Chem. Commun Volume: 48 Issue: 45 Pages: 5629-5631
  • DOI: 10.1039/c2cc31955a
  • Peer Reviewed
• [Journal Article] Morofuji, T.; Shimizu, A.; Yoshida, J (2012)
  • Author(s): Metal- and Chemica-Oxidant-Free C-H/C-H Cross- Coupling of Aromatic Compounds Using "Radical Cation Pools"
  • Journal Title: Angew. Chem. Int. Ed Volume: 51 Issue: 29 Pages: 7259-7262
  • DOI: 10.1002/anie.201202788
  • Peer Reviewed
• [Journal Article] Polymer-Bound Pyrene-4,5,9,10-tetraone for Fast-Charge and-Discharge Lithium-Ion Batteries with High Capacity. (2012)
  • Author(s): Nokami, T.; Matsuo, T.; Inatomi, Y.; Hojo, N.; Tsukagoshi, T.; Yoshizawa, H.; Shimizu, A.; Kuramoto, H.; Komae, K.; Tsuyama, H.; Yoshida, J.
  • Journal Title: J. Am. Chem. Soc. Volume: 134 Issue: 48 Pages: 19694-19700
  • DOI: 10.1021/ja306663g
  • Peer Reviewed
• [Journal Article] Experimental consideration of covalent bonding interactions in stacks of singlet biradicals having Kekule structures (2011)
  • Author(s): 清水章弘
  • Journal Title: J.Phys.Org.Chem. Volume: 24 Issue: 10 Pages: 876-882
  • DOI: 10.1002/poc.1873
  • Peer Reviewed
• [Journal Article] Indeno[2,1-a]fluorene: An Air-Stable ortho-Quinodimethane Derivatives (2011)
  • Author(s): Shimizu, A.; Tobe, Y.
  • Journal Title: Angew. Chem. Int. Ed. Volume: 50 Issue: 30 Pages: 6906-6910
  • DOI: 10.1002/anie.201101950
  • Peer Reviewed
• [Journal Article] Synthesis, Crystal Structure and Physical Properties of Sterically Unprotected Hydrocarbon Radicals (2011)
  • Author(s): T.Kubo
  • Journal Title: J.Am.Chem.Soc. Volume: 133 Issue: 36 Pages: 14240-14243
  • DOI: 10.1021/ja2065768
  • Peer Reviewed
• [Presentation] C-H/C-H Cross-Coupling of Aromatic Compounds Using Electrochemically Generated "Radical Cation Pools" (2013)
  • Author(s): Shimizu, A
  • Organizer: The First Bristol-Kyoto Symposium
  • Place of Presentation: ブリストル大学 イギリス
  • Year and Date: 2013-01-11
• [Presentation] C-H/C-H Cross-Coupling of Aromatic Compounds Using Electrochemically Generated "Radical Cation Pools" (2013)
  • Author(s): Shimizu, A.
  • Organizer: The First Bristol-Kyoto Symposium
  • Place of Presentation: ブリストル大学
• [Presentation] 電解酸化による芳香族第一級アミンの合成 (2013)
  • Author(s): 諸藤達也・清水章弘・吉田潤一
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学草津キャンパス
• [Presentation] 電解酸化による芳香族化合物のC－Hアミノ化 (2013)
  • Author(s): 諸藤達也・清水章弘・吉田潤一
  • Organizer: 電気化学会創立第80周年記念大会
  • Place of Presentation: 東北大学川内キャンパス
• [Presentation] 金属・酸化剤を用いない芳香族化合物のC-H/C-H クロスカップリング (2012)
  • Author(s): 諸藤達也・清水章弘・吉田潤一
  • Organizer: 第1回 JACI/GSCシンポジウム（第12回 GSCシンポジウム）
  • Place of Presentation: ベルサール神田
• [Presentation] ラジカルカチオンプール法による芳香族化合物の脱水素型クロスカップリング (2012)
  • Author(s): 諸藤達也・清水章弘・吉田潤一
  • Organizer: 第36回有機電子移動討論会
  • Place of Presentation: ルミエール府中
• [Presentation] C-H/C-H Cross-Coupling of Aromatic Compounds Based on the “Radical-Cation Pool” Method (2012)
  • Author(s): Morofuji, T.; Shimizu, A.; Yoshida, J.
  • Organizer: IKCOC-12
  • Place of Presentation: リーガロイヤル京都
• [Presentation] ジゼトレニルアセチレンの合成 (2012)
  • Author(s): 北林賢一・日比大治郎・清水章弘・戸部義人
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 神奈川、慶應義塾大学
• [Presentation] 電子移動による芳香族化合物の酸化的クロスカップリング (2012)
  • Author(s): 諸藤達也・清水章弘・吉田潤一
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 神奈川、慶應義塾大学
• [Presentation] 環状ビシナルジケトン類の電気化学特性 (2012)
  • Author(s): 松尾隆宏・清水章弘・野上敏材・吉田潤一
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 神奈川、慶應義塾大学
• [Presentation] インデノフルオレンの特徴的な電子構造の解明 (2012)
  • Author(s): 清水章弘・岸亮平・中野雅由・塩見大輔・佐藤和信・工位武治・戸部義人
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 神奈川、慶應義塾大学
• [Presentation] インデノフルオレンの特徴的な電子構造の解明 (2011)
  • Author(s): 清水章弘, 岸亮平, 中野雅由, 塩見大輔, 佐藤和信, 工位武治, 戸部義人
  • Organizer: 日本化学会第92 春季年会
  • Place of Presentation: 神奈川
  • Year and Date: 2011-03-28
• [Presentation] Indenofluorene Isomers: 6-5-6-5-6 Membered Ring Hydrocarbons with Singlet Biradical Character (2011)
  • Author(s): Yoshito Tobe, Akihiro Shimizu
  • Organizer: 14th International Symposium on Novel Aromatic Compounds (ISNA 14)
  • Place of Presentation: Oregon, USA
• [Presentation] Formation of Unprecedented Polycyclic Aromatic Hydrocarbons by BuLi-induced Tandem Cyclization of Dehydrobenzo[14]annulene (2011)
  • Author(s): Shunpei Nobusue, Akihiro Shimizu, Kazukuni Tahara, Yoshito Tobe
  • Organizer: 14th International Symposium on Novel Aromatic Compounds (ISNA 14)
  • Place of Presentation: Oregon, USA
• [Presentation] Highly Delocalized Polycyclic Aromatic Hydrocarbon (PAH) Radical (2011)
  • Author(s): Takashi Kubo, Yoshiki Katada, Akihiro Shimizu, Yasukazu Hirao, Kouzou Matsumoto, Hiroyuki Kurata, Robert C. Haddon
  • Organizer: 14th International Symposium on Novel Aromatic Compounds (ISNA 14)
  • Place of Presentation: Oregon, USA
• [Presentation] The Singlet Open-shell Character of Anthenes: Synthesis and Characterization of Quarteranthene (2011)
  • Author(s): Akihito Konishi, Akihiro Shimizu, Yasukazu Hirao, Kouzou Matsumoto, Hiroyuki Kurata, Takashi Kubo, Masayoshi Nakano, Benoît Champagne
  • Organizer: 14th International Symposium on Novel Aromatic Compounds (ISNA 14)
  • Place of Presentation: Oregon, USA
• [Presentation] ブチルリチウムの付加により誘起されるデヒドロベンゾ[14]アヌレン類の渡環環化による環状インデノフルオレン二量体の生成 (2011)
  • Author(s): 信末俊平・清水章弘・田原一邦・戸部義人
  • Organizer: 第22回基礎有機化学討論会
  • Place of Presentation: 茨城、つくば国際会議場
• [Presentation] ヘプタゼトレン誘導体の合成 (2011)
  • Author(s): 日比大治郎・清水章弘・戸部義人
  • Organizer: 第22回基礎有機化学討論会
  • Place of Presentation: 茨城、つくば国際会議場
• [Presentation] Indeno[2,1-a]fluorene Dimers Formed by Transannular Cyclization of Dehydrobenzo[14]annulene (2011)
  • Author(s): Shunpei Nobusue, Akihiro Shimizu, Kazukuni Tahara, Yoshito Tobe
  • Organizer: The Seventh International Symposium on Integrated Synthesis (ISIS-7)
  • Place of Presentation: Kobe、Seaside Hotel Maiko Villa
• [Presentation] オクタデヒドロベンゾ[12]アヌレンへの求核剤の付加により誘起される渡環環化 (2011)
  • Author(s): 吉崎亜由美・信末俊平・清水章弘・戸部義人
  • Organizer: 第5回有機π電子系シンポジウム
  • Place of Presentation: 大阪、ホテルアウィーナ大阪
• [Presentation] ジゼトレニルアセチレンの合成 (2011)
  • Author(s): 北林賢一・日比大治郎・清水章弘・戸部義人
  • Organizer: 第5回有機π電子系シンポジウム
  • Place of Presentation: 大阪、ホテルアウィーナ大阪
• [Book] World Scientific (2011)
  • Author(s): Shimizu, A.; Konishi, A.; Hirao, Y.; Kubo, T
  • Publisher: Singlet Open-Shell Character of polyperiacenes.
• [Book] Chapter 3: Singlet Open-Shell Character of polyperiacenes, in GRAPHENE AND ITS FASCINATING ATTRIBUTES, Swapan K Pati, Toshiaki Enoki, C N R Rao (2011)
  • Author(s): Akihiro Shimizu, Akihito Konishi, Yasugazu Hirao, Takashi Kubo
  • Total Pages: 270
  • Publisher: World Scientific
• [Remarks]
  • URL: http://www.sbchem.kyoto-u.ac.jp/yoshida-lab/index