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

2012 Fiscal Year Final Research Report

• 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
• 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

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 After TandemCyclization of Dehydrobenzo[14]annulenes Induced by Alkyllithium. (2013)
  • Author(s): Nobusue, S.; Shimizu, A.; Hori, K.; Hisaki, I.; Miyata, M.; Tobe, Y.
  • Journal Title: Angew. Chem. Int. Volume: 52 Pages: 4184-4188
  • DOI: DOI:10.1002/anie.201210233
  • Peer Reviewed
• [Journal Article] Morofuji, T.; Shimizu, A.; Yoshida, J (2013)
  • Author(s): Electrochemical C-H Amination: Synthesis of Aromatic Primary Amines via N-Arylpyridinium Ions.
  • Journal Title: J. Am. Chem. Soc Volume: 135 Pages: 5000-5003
  • DOI: DOI:10.1002/10.1021/ja402083e
  • Peer Reviewed
• [Journal Article] Indeno[2,1,-b]fluorene: A 20π Electron Hydrocarbon with Very Low Energy Light Absorption. (2013)
  • Author(s): Shimizu, A.; Kishi, R.; Nakano, M.; Shiomi, D.; Sato, K.; Takui, T.; Hisaki, I.; Miyata, M.; Tobe, Y.
  • Journal Title: Angew. Chem. Int Volume: 52 Pages: 6076-6079
  • DOI: 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): Shimizu, A.; Hirao, Y.; Kubo, T.; Nakano,M.; Botek, E.; Champagne, B
  • Journal Title: AIP Conf. Proc Volume: 1504 Pages: 399-405
  • DOI: 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): Champagne, B.; Botek, E.; Shimizu, A.; Kubo, T.; Kamada, K.; Ohta, K.; Kishi, R.; Fukui, H.; Takahashi, H.; Nakano, M.
  • Journal Title: AIP Conf. Proc Volume: 1504 Pages: 844-847
  • DOI: DOI:10.1063/1.4771826
  • Peer Reviewed
• [Journal Article] Singlet Open-Shell Character of Conjugated Kekule Molecules. (2012)
  • Author(s): Kubo, T.; Aoba, M.; Shimizu, A.; Hirao, Y.; Matsumoto, K.; Kurata, H.; Nakano, M
  • Journal Title: AIP Conf. Proc Volume: 1504 Pages: 883-886.
  • DOI: 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 Pages: 5629-5631
  • DOI: DOI:10.1039/C2CC31955A
  • Peer Reviewed
• [Journal Article] Metal- and Chemical-Oxidant-Free C-H/C-H Cross-Coupling of Aromatic Compounds: The Use of Radical-Cation Pools. (2012)
  • Author(s): Morofuji, T.; Shimizu, A.; Yoshida, J
  • Journal Title: Angew.Chem. Int Volume: 51 Pages: 7259-7262.
  • DOI: 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.Nokami (2012)
  • Author(s): 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 Pages: 19694-19700.
  • DOI: DOI:10.1021/ja306663g
  • Peer Reviewed
• [Journal Article] Experimental consideration of covalent bonding interactions in stacks of singlet biradicals (2011)
  • Author(s): Shimizu, A.; Nakano, M.; Hirao, Y.; Kubo, T
  • Journal Title: J. Phys. Org. Chem Volume: 24 Pages: 876-882.
  • DOI: DOI:10.1002/poc.1873
  • Peer Reviewed
• [Journal Article] Indeno[2,1-a]fluorene: An Air-Stableortho-Quinodimethane (2011)
  • Author(s): Shimizu, A.; Tobe, Y
  • Journal Title: Angew. Chem. In Volume: 50 Pages: 6906-6910
  • DOI: DOI:10.1002/anie.201101950
  • Peer Reviewed
• [Journal Article] Synthesis, Crystal Structure, and Physical Properties of Sterically Unprotected Hydrocarbon RadicalsKubo, T (2011)
  • Author(s): Katada, Y.; Shimizu, A.; Hirao, Y.; Sato,K.; Takui, T.; Uruichi, M.; Yakushi, K.; Haddon, R. C
  • Journal Title: J. Am. Chem. Soc Volume: 133 Pages: 14240 -14243
  • DOI: 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] 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
• [Book] World Scientific (2011)
  • Author(s): Shimizu, A.; Konishi, A.; Hirao, Y.; Kubo, T
  • Total Pages: 45-57
  • Publisher: Singlet Open-Shell Character of polyperiacenes.
• [Remarks]
  • URL: http://www.sbchem.kyoto-u.ac.jp/yoshida-lab/index