Development of three-dimensional pi-electronic compounds originated from tripyrrin subunits

• Project/Area Number: 24750034
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Shimane University (2014); Chiba University (2012-2013)
• Principal Investigator: SUZUKI Masaaki 島根大学, 総合理工学研究科(研究院), 講師 (90506891)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2014: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2013: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2012: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: ポルフィリノイド / 環拡張ポルフィリン / ペンタフィリン / 芳香族性 / トリフルオロメチル化 / 求核置換反応

Outline of Final Research Achievements

The major target of this project utilizing tripyrrine precursors was switched to development of a wide variety of three-dimensional π-systems. As a result, it was successfully achieved that novel three-dimensionalπ-electronic modes bearing a branchedπ-plane had been constructed based on peculiar nucleophilic substitution reactions onto recombined N-fused pentaphyrin bromide. In the meantime, meso-trifluoromethyl substituted octaalkylporphyrins were obtained by scrambling side reactions of oligo-pyrrolic precursors. The strongly electron-withdrawing nature and the spatial steric hindrance of trifluoromethyl group caused a large distortion of the macrocyclic plane and improvement of the absorption property. Furthermore, the trifluoromethyl groups undertook solvolysis when the centeral metal ion was zinc, affording meso-methoxycarbonyl derivatives.

Research Products

• [Journal Article] 5,20-Bis(α-Oligothienyl)-Substituted [26]Hexaphyrins(1.1.1.1.1.1): 26π Aromatic Hexaphyrin Circuit versus Acyclic Helical Conjugation (2015)
  • Author(s): Hirotaka Mori, Masaaki Suzuki, Woojae Kim, Jong Min Lim, Dongho Kim, Atsuhiro Osuka
  • Journal Title: Chemical Science Volume: 6 Issue: 3 Pages: 1696-1700
  • DOI: 10.1039/c4sc03394a
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Skeletal recombination reaction of N-fused pentaphyrin(1,1,1,1,1) via bromination (2014)
  • Author(s): Masaaki Suzuki, Tyuji Hoshino, and Saburo Neya.
  • Journal Title: Org Lett Volume: 16 Issue: 2 Pages: 327-329
  • DOI: 10.1021/ol403242z
  • Peer Reviewed
• [Journal Article] Syntheses of Highly Distorted meso-Trifluoromethyl-Substituted β-Octaalkylporphyrins (2014)
  • Author(s): Masaaki Suzuki, Shuto Ishii, Tyuji Hoshino, Saburo Neya
  • Journal Title: Chem. Lett. Volume: 43 Issue: 10 Pages: 1563-1565
  • DOI: 10.1246/cl.140561
  • NAID: 130004427212
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Computational and statistical study on the molecular interaction between antigen and antibody (2014)
  • Author(s): T. Osajima, M. Suzuki, S. Neya, T. Hoshino
  • Journal Title: J. Mol. Graphics Model. Volume: 53 Pages: 128-139
  • DOI: 10.1016/j.jmgm.2014.07.005
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Ralaxation analysis of ligand binding to the myoglobin reconstituted with cobartic heme. (2013)
  • Author(s): Neya S, Suzuki M, Hoshino T, Kawaguchi AT.
  • Journal Title: Inorganic Chemistry Volume: 52 Issue: 13 Pages: 7387-7393
  • DOI: 10.1021/ic400078w
  • Peer Reviewed
• [Journal Article] Deprotonation-Induced Aromaticity Enhancement and New Conjugated Networks in meso-Hexakis(pentafluorophenyl)[26]hexaphyrin (2012)
  • Author(s): W.-Y. Cha, J. M. Lim, M.-C. Yoon, Y. M. Sung, B. S. Lee, S. Katsumata, M. Suzuki, H. Mori, A. Osuka, Y. Ikawa, H. Furuta, and D. Kim
  • Journal Title: Chem. Eur. J Volume: 18 Issue: 49 Pages: 15838-15844
  • DOI: 10.1002/chem.201200991
  • Peer Reviewed
• [Presentation] 非環状らせん共役系を有するヘキサフィリンの合成と物性 (2015)
  • Author(s): 森裕貴，鈴木優章，大須賀篤弘
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学理工学部船橋キャンパス（船橋）
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] 非平面meso-トリフルオロメチル置換β-オクタアルキルポルフィリンの合成と物性 (2014)
  • Author(s): 鈴木優章，石井修人，星野忠次，根矢三郎
  • Organizer: 第25回基礎有機化学討論会
  • Place of Presentation: 東北大学川内北キャンパス（仙台）
  • Year and Date: 2014-09-07 – 2014-09-09
• [Presentation] Porphyrin with a Terpyridine Coordination Unit as the Imaging Probe for SPECT (2014)
  • Author(s): Saburo Neya, Masaaki Suzuki
  • Organizer: 8ｔｈ International Conference on Porphyrins and Phthalocyanines
  • Place of Presentation: トルコ（イスタンブール）
  • Year and Date: 2014-06-22 – 2014-06-27
• [Presentation] Skeletally recombined N-fused pentaphyrin(1.1.1.1.1) bromide and its derivatives (2014)
  • Author(s): Masaaki Suzuki, Tyuji Hoshino, Saburo Neya
  • Organizer: 8ｔｈ International Conference on Porphyrins and Phthalocyanines
  • Place of Presentation: トルコ（イスタンブール）
  • Year and Date: 2014-06-22 – 2014-06-27
• [Presentation] 人工酸素運搬体素材としてのミオグロビンの分子設計 (2014)
  • Author(s): 根矢三郎・鈴木優章・星野忠次
  • Organizer: 日本薬学会第１３４年会
  • Place of Presentation: 熊本大学
• [Presentation] N-フューズドペンタフィリンの骨格変換と分子内π拡張反応 (2013)
  • Author(s): 鈴木優章・星野忠次・根矢三郎
  • Organizer: 第２４回基礎有機化学討論会
  • Place of Presentation: 学習院大学目白ｷｬﾝﾊﾟｽ
• [Presentation] 臭素化を経由するN-フューズドペンタフィリンの骨格変換 (2013)
  • Author(s): 鈴木優章，星野忠次，根矢三郎
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 草津
• [Presentation] 緩和法による酸化型コバルトを含むミオグロビンへの配位子結合解析 (2013)
  • Author(s): 根矢三郎，星野忠次，鈴木優章，川口章
  • Organizer: 日本薬学会第133年会
  • Place of Presentation: 横浜
• [Presentation] インフルエンザエンドヌクレアーゼ活性阻害化合物の探索とその結合構造解析 (2013)
  • Author(s): 8. 不動聡志，石井和彦，小川博史，松浦崇晃，柳田浩，額賀路嘉，鈴木優章，根矢三郎，星野忠次
  • Organizer: 日本薬学会第133年会
  • Place of Presentation: 横浜
• [Presentation] Synthesis, Structure, and Aromaticity of the Ni(II) Complex of Pyricorrole, a New Porphyrin Isomer (2012)
  • Author(s): Neya, S., Suzuki, M., Matsugae, T., Hoshino, T.
  • Organizer: 22回金属の関与する生体関連反応シンポジウム
  • Place of Presentation: 金沢
• [Presentation] Geometric and Electronic Structures of Nickel(II) Pyricorrole: Hybridization of Porphyrin and Corrole (2012)
  • Author(s): Neya, S., Suzuki, M., Matsugae, T., Hoshino, T.
  • Organizer: 7th International Conference on Porphyrins and Phthalocyanines
  • Place of Presentation: 韓国Jeju
• [Presentation] Amining at application of expanded porphyrin expecially for medicinal use (2012)
  • Author(s): Suzuki, M., Hoshino, T., Neya, S.
  • Organizer: 7th International Conference on Porphyrins and Phthalocyanines
  • Place of Presentation: 韓国Jeju
• [Presentation] 臭素化を経由するN-フューズドペンタフィリンの骨格変換 (2012)
  • Author(s): 鈴木優章，星野忠次，根矢三郎
  • Organizer: 第23回基礎有機化学討論会
  • Place of Presentation: 京都
• [Presentation] 新規ポルフィリン異性体ピリコロールの合成と電子状態解析 (2012)
  • Author(s): 根矢三郎，鈴木優章，星野忠次
  • Organizer: 錯体化学会第62回討論会
  • Place of Presentation: 富山
• [Presentation] ヨウ素NMR スペクトルによる有機化合物の同定
  • Author(s): 加川夏子・鈴木優章・小暮紀行
  • Organizer: 第１ ６回 ヨウ素学会シンポジム
  • Place of Presentation: 千葉大学けやき会館