Development of Novel π-Conjugated Systems Based on Porphyrins

• Project/Area Number: 19205006
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Kyoto University
• Principal Investigator: OSUKA Atsuhiro Kyoto University, 大学院・理学研究科, 教授 (80127886)
• Project Period (FY): 2007 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥45,500,000 (Direct Cost: ¥35,000,000、Indirect Cost: ¥10,500,000); Fiscal Year 2009: ¥15,340,000 (Direct Cost: ¥11,800,000、Indirect Cost: ¥3,540,000); Fiscal Year 2008: ¥15,080,000 (Direct Cost: ¥11,600,000、Indirect Cost: ¥3,480,000); Fiscal Year 2007: ¥15,080,000 (Direct Cost: ¥11,600,000、Indirect Cost: ¥3,480,000)
• Keywords: ポルフィリン / 環拡張ポルフィリン / ポルフィリンテープ / メビウス芳香族性 / 芳香族性 / 2光子吸収断面積 / 反芳香族性 / 共役

Research Abstract

We have achieved strong 4nπ Mobius aromaticity by various methods for the conformational control of meso-aryl expanded porphyrins, such as metal coordination, temperature control, protonation, and intramoleculer fusion. We report the syntheses of a series of novel subporphyrins and related molecules by various chemical transformations of meso-aryl-subporphyrins. In addition, we have also developed a transition metal-catalyzed coupling reactions toward the construction of multi-porphyrin arrays.

Research Products

• [Journal Article] Bithiophene-Porphyrin Hybrid Nanorings (2010)
  • Author(s): K. Osawa, J. Song, K. Furukawa, H. Shinokubo, N. Aratani, A. Osuka
  • Journal Title: Chem. Asian J. 5巻 Pages: 764-767
  • Peer Reviewed
• [Journal Article] Strategic Synthesis of 2, 6-Pyridylene-Bridged β-to-βPorphyrin Nanorings through Cross-Coupling (2010)
  • Author(s): J. Song, P. Kim, N. Aratani, D. Kim, H. Shinokubo, A. Osuka
  • Journal Title: Chem. Eur. J. 16巻 Pages: 3009-3012
  • Peer Reviewed
• [Journal Article] Fullyπ-Conjugated Helices from Oxidative Cleavage of meso-Aryl-Substituted Expanded Porphyrins (2010)
  • Author(s): S. Saito, K. Furukawa, A. Osuka
  • Journal Title: J. Am. Chem. Soc. 132巻 Pages: 2128-2129
  • Peer Reviewed
• [Journal Article] Meso-Trialkyl-Substituted Subporphyrins (2010)
  • Author(s): S. Hayashi, Y. Inokuma, S. Easwaramoorthi, K.S. Kim, D. Kim, A. Osuka
  • Journal Title: Angew. Chem. Int. Ed. 49巻 Pages: 321-324
  • Peer Reviewed
• [Journal Article] Phosphorus Complexes of the First Expanded Isophlorins (2010)
  • Author(s): T. Miura, T. Higashino, S. Saito, A. Osuka
  • Journal Title: Chem. Eur. J. 16巻 Pages: 55-59
  • Peer Reviewed
• [Journal Article] Fully π-Conjugated Helices from Oxidative Cleavage of meso-Aryl Substituted Expanded Porphyrins (2010)
  • Author(s): S.Saito, K.Furukawa, A.Osuka
  • Journal Title: J.Am.Chem.Soc. 132 Pages: 2128-2129
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Dimerization of meso-Bromoporphyrins: Highly Regioselective meso-βCoupling through Unprecedented Remote C-H Bond Cleavage (2009)
  • Author(s): S. Tokuji, T. Yurino, N. Aratani, H. Shinokubo, A. Osuk
  • Journal Title: Chem. Eur. J. 15巻 Pages: 12208-12211
  • Peer Reviewed
• [Journal Article] T-shaped Three-Coordinate Copper (II) Heptaphyrin Complexes (2009)
  • Author(s): S. Saito, K. Furukawa, A. Osuka
  • Journal Title: Angew. Chem. Int. Ed. 48巻 Pages: 8086-8089
  • Peer Reviewed
• [Journal Article] Thermal Fusion Reactions of meso-(3-Thienyl) Groups in [26]Hexaphyrins to Produce Mobius Aromatic Molecules (2009)
  • Author(s): M. Inoue, K.S. Kim, M. Suzuki, J.M. Lim, J.-Y. Shin, D. Kim, A. Osuka
  • Journal Title: Angew. Chem. Int. Ed. 48巻 Pages: 6687-66890
  • Peer Reviewed
• [Journal Article] Facile Formation of a Benzopyrane-Fused [28] Hexaphyrin That Exhibits Distinct Mobius Aromaticity (2009)
  • Author(s): S. Tokuji, J.-Y. Shin, K.S. Kim, J.M. Lim, K. Youfu, S. Saito, D. Kim, A. Osuka
  • Journal Title: J. Am. Chem. Soc. 131巻 Pages: 7240-7241
  • Peer Reviewed
• [Journal Article] Zwitterionic Corroles: Regioselective Nucleophilic Pyridination of a Doubly Linked Biscorrole (2009)
  • Author(s): S. Hiroto, N. Aratani, N. Shibata, Y. Higuchi, T. Sasamori, N. Tokitoh, S. Shinokubo, A. Osuka
  • Journal Title: Angew. Chem. Int. Ed. 48巻 Pages: 2388-2390
  • Peer Reviewed
• [Journal Article] Peripheral Hexabromination, Hexaphenylation, and Hexaethynylation of meso-Aryl Substituted Subporphyrins (2009)
  • Author(s): E. Tsurumaki, Y. Inokuma, S. Easwaramoorthi, J.M. Lim, D. Kim, A. Osuka
  • Journal Title: Chem. Eur. J. 15巻 Pages: 237-247
  • Peer Reviewed
• [Journal Article] Capped Subporphyrins (2009)
  • Author(s): Y.Inokuma, A.Osuka
  • Journal Title: Chem. Eur. J. 15 Pages: 6863-6876
  • Peer Reviewed
• [Journal Article] Facile Formation of a Benzopyrane-Fused [28] Hexaphyrin That Exhibits Distinct Mobius Aromaticity (2009)
  • Author(s): S.Tokuji, J.-Y.Shin, K.S.Kim, J.M.Lim, K.Youfu, S.Saito, D.Kim, A.Osuka
  • Journal Title: J.Am.Chem.Soc. 131 Pages: 7240-7241
  • Peer Reviewed
• [Journal Article] Synthesis of Directly and Doubly Linked Dioxoisobacteriochlorin Dimers" (2008)
  • Author(s): S. Hiroto, I. Hisaki, H. Shinokubo, A. Osuka
  • Journal Title: J. Am. Chem. Soc. 130巻 Pages: 16172-16173
  • Peer Reviewed
• [Journal Article] A Stable Radical from Facile Oxygenation of meso-Free 5, 10, 20, 25-Tetrakis (pentafluorophenyl) Substituted [26] Hexaphyrin (1. 1. 1. 1. 1. 1) (2008)
  • Author(s): T. Koide, G. Kashiwazaki, M. Suzuki, K. Furukawa, M.-C. Yoon, S. Cho, D. Kim, A. Osuka
  • Journal Title: Angew. Chem. Int. Ed. 47巻 Pages: 9661-9665
  • Peer Reviewed
• [Journal Article] Protonation-Triggered Conformational Changes to Mobius Aromatic [32] Heptaphyrins (1. 1. 1. 1. 1. 1. 1) (2008)
  • Author(s): S. Saito, J.Y. Shin, J.M. Lim, K.S. Lim, D. Kim, A. Osuka
  • Journal Title: Angew. Chem. Int. Ed. 47巻 Pages: 9657-9660
  • Peer Reviewed
• [Journal Article] Pt (II)-and Pt (IV)-Bridged Cofacial Diporphyrins via Carbon-Transition Metalσ-Bonds (2008)
  • Author(s): S. Yamaguchi, T. Katoh, H. Shinokubo, A. Osuka
  • Journal Title: J. Am. Chem. Soc. 130巻 Pages: 14440-14441
  • Peer Reviewed
• [Journal Article] Unambiguous Identification of Mobius Aromaticity for meso-Aryl Substituted [28]Hexaphyrins (1. 1. 1. 1. 1. 1) (2008)
  • Author(s): J. Sankar, S. Mori, S. Saito, H. Rath, M. Suzuki, Y. Inokuma, H. Shinokubo, K.S. Kim, Z.S. Yoon, J.-Y. Shin, J.M. Lim, Y. Matsuzaki, O. Matsushita, A. Muranaka, N. Kobayashi, D. Kim, A. Osuka
  • Journal Title: J. Am. Chem. Soc. 130巻 Pages: 13568-13579
  • Peer Reviewed
• [Journal Article] Two-Dimensionally Extended Porphyrin Tapes: Synthesis and Shape-Dependent Two-Photon Absorption Properties (2008)
  • Author(s): Y. Nakamura, S.Y. Yang, T. Tanaka, N. Aratani, J.M. Lim, K.S. Kim, D. Kim, A. Osuka
  • Journal Title: Chem. Eur. J. 14巻 Pages: 8279-8289
  • Peer Reviewed
• [Journal Article] meso-(4-(N, N-Dialkylamino)pheny1)-Substituted Subporphyrins: Remarkably Perturbed Absorption Spectra and Enhanced Fluorescence by Intramolecular Charge Transfer Interactions (2008)
  • Author(s): Y. Inokmua, S. Easwaramoorthi, Z.S. Yoon, D. Kim, A. Osuka
  • Journal Title: J. Am. Chem. Soc. 130巻 Pages: 12234-12235
  • Peer Reviewed
• [Journal Article] A meso洋eso directly linked octameric porphyrin square (2008)
  • Author(s): N. Aratani, A. Osuka
  • Journal Title: Chem. Commun. Pages: 4067-4069
  • Peer Reviewed
• [Journal Article] 2, 5-Thienylene-Bridged Triangular and Linear Porphyrin Trimers (2008)
  • Author(s): J. Song, S.Y. Jang, S. Yamaguchi, J. Sankar, S. Hiroto, N. Aratani, J.-Y. Shin, S. Easwaramoorthi, K.S. Kim, D. Kim, H. Shinokubo, A. Osuka
  • Journal Title: Angew. Chem. Int. Ed. 47巻 Pages: 6004-6007
  • Peer Reviewed
• [Journal Article] Unambieuous Identification or mobius Aromaticity for meso-Aryl-Siibstituted [28]Hexaphyrins(1.1.1.1.1.1) (2008)
  • Author(s): J. Sankar
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 13568-13579
  • Peer Reviewed
• [Journal Article] Protonation-triggered Conformational Changed to Mobius Aromatic [32]Heptapliyrins(1.1.1.1.1.1.1) (2008)
  • Author(s): S. Saito
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 9657-9660
  • Peer Reviewed
• [Journal Article] A Stable Radical Species from Facile Oxvgenation of meso-Free5, 10, 20, 25-Tetrakis(pentafluorophenyl)-Substituted [26]Hexaphyrin(1.1.1.1.1.1) (2008)
  • Author(s): T. Koide
  • Journal Title: Angew. Chem. Int. Ed. 17 Pages: 9661-9665
  • Peer Reviewed
• [Journal Article] Metakation of Expanded Porphyrins: A Chemical Trigger Used to Produce Molecular Twisting and Mobius Aromaticity (2008)
  • Author(s): Y. Tanaka, et. al.
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 681-684
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of meso-Aryl-Substituted Subchlorins (2008)
  • Author(s): E. Tsurumaki
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 438-439
  • Peer Reviewed
• [Journal Article] Peripehral Fabrications of a Bis-Gold(III) Complex of [26] Hexaphyrin(1.1.1.1.1.1) (2007)
  • Author(s): S. Mori
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 11344-11345
  • Peer Reviewed
• [Presentation] Exploration of Novel Porphyrinoids (2009)
  • Author(s): 大須賀篤弘
  • Organizer: Universidad Autonoma de Madrid
  • Place of Presentation: スペイン・マドリッド
  • Year and Date: 2009-07-02
• [Presentation] ポルフィリンの化学-驚きに魅せられて (2009)
  • Author(s): 大須賀篤弘
  • Organizer: 名古屋大学GCOE化学セミナー
  • Place of Presentation: 名古屋
  • Year and Date: 2009-05-18
• [Presentation] 新しいポルフィリンの合成と光物性 (2009)
  • Author(s): 大須賀篤弘
  • Organizer: 特定領域研究「光-分子強結合場」研究代表者三澤弘明
  • Place of Presentation: 京都
  • Year and Date: 2009-05-08
• [Presentation] Maius aromatic Expanded Porphyrins (2009)
  • Author(s): 大須賀篤弘
  • Organizer: Pre-strategic Initiative Symposium on Creation of Functional Molecules, Invited Lecture
  • Place of Presentation: 筑波
• [Presentation] 環拡張ポルフィリンの金属錯体 (2009)
  • Author(s): 大須賀篤弘
  • Organizer: 2009錯体化学討論会シンポジウム
  • Place of Presentation: 長崎
• [Presentation] 新しいポルフィリンの合成と光物性 (2009)
  • Author(s): 大須賀篤弘
  • Organizer: 2009光化学討論会
  • Place of Presentation: 桐生
• [Presentation] ovalently and Noncovalently Linked Porphyrin Arrays (2009)
  • Author(s): 大須賀篤弘
  • Organizer: 42th IUPAC Congress: Chemistry Solutions
  • Place of Presentation: グラスゴー
• [Presentation] Exploration of Novel Porphyrinoids with Interesting Electronic Properties: Aromaticity and Topology (2009)
  • Author(s): 大須賀篤弘
  • Organizer: the 2009 NOZOE MEMORIAL LECTURE, 13th International Symposium on Novel Aromatic Compounds (ISNA-13)
  • Place of Presentation: ルクセンブルク
• [Presentation] Mobius Aromatic Expanded Porphyrins (2009)
  • Author(s): 大須賀篤弘
  • Organizer: 10th International Conference on Calixarenes (ICC)
  • Place of Presentation: ソウル
• [Presentation] Mobius Aromatic Expanded Porphyrins (2009)
  • Author(s): 大須賀篤弘
  • Organizer: Invited Lecture, 2009 International Symposium on Reactive Intermediates and Unusual Molecules
  • Place of Presentation: チェコ
• [Book] 配位空間の化学・第IV編第3章・自己識別会合 (2009)
  • Author(s): 荒谷直樹・大須賀篤弘, 北川進監修
  • Publisher: CMC出版
• [Remarks]
  • URL: http://kuchem.kyoto-u.ac.jp/shuyu