集合化を特徴とする動的酸化還元系分子の集積合成：次元的秩序性の外部刺激制御

2013 Fiscal Year Annual Research Report

• Project Area: Organic Synthesis based on Integration of Chemical Reactions. New Methodologies and New Materials
• Project/Area Number: 21106012
• Research Institution: Hokkaido University
• Principal Investigator: 鈴木 孝紀 北海道大学, 理学(系)研究科(研究院), 教授 (70202132)
• Project Period (FY): 2009-07-23 – 2014-03-31
• Keywords: クロミズム応答 / 酸化還元 / 集積合成

Research Abstract

本年度は、本新学術領域の複数の研究グループと共同研究を実施することで、集積型合成を駆使して得られるようになった化合物群の機能開発および特異な構造探索を行なうこととした。具体的な共同研究先は、1)京都大学　吉田研究室(A01班、領域代表)、2）京都大学　大野研究グループ(A02班、公募班員)、3)北海道大学　谷野研究室（A02班、計画班員）、4)慶応義塾大学　垣内研究室（A01班、公募班員）である。
上記4つの研究グループとの共同研究を通じて、1)　非対称テトラアリールピラセン誘導体のフローマイクロリアクター合成を吉田研究室永木講師の指導のもとで行い、極度に伸長したC-C結合長の"expadability"という特性に対する更なる調査を進め、非対称に置換したMeO,F置換化合物が、複数の擬多形結晶中で異なる結合長を示す現象を見出した；2）金触媒反応を鍵とする連続環化によって大野研究グループで新たに合成された強蛍光性縮環カルバゾール類について、その酸化還元挙動やスペクトル特性を調査し、NIRまで吸収を持つカチオンラジカル種の単離やそのX線構造解析を行なうとともに、多重クロミズム応答機能の開発に成功した；3)ジビニルシクロプロパンの転位反応を利用した新規アズレン合成法に基づく両性酸化還元系の開発に成功した；4)同一空間かつ時間的反応集積化を活用して垣内研究室で合成されたビフェニル-2,2'-ジイルビピリジンを用いた、新規な動的酸化還元骨格の開発を検討中である。
1)については、本領域成果報告会を兼ねた国際学会ISIS-8で発表しており、また論文発表もなされている。２、3）も既に論文発表されている、4）は現在進行中であるが、着想に関する論文は、ごく最近発表された。

Current Status of Research Progress

Reason

25年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

25年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Chiral Memory Units Based on Dynamic Redox Systems with a Dibenzoepinone Skeleton (2014)
  • Author(s): K. Wada, Y. Chiba, T. Takeda, H. Kawai, R. Katoono, K. Fujiwara, T. Suzuki
  • Journal Title: Heterocycles Volume: 88(2) Pages: 945-952
  • Peer Reviewed
• [Journal Article] Expandability of Ultralong C-C Bond: Largely Different C1-C2 Bond Length Determined by Low-temperature X-ray Analyses on Pseudopolymorphs of 1,1-Bis(4-fluorophenyl)-2,2-bis(4-methoxyphenyl)pyracene, (2014)
  • Author(s): T. Suzuki, Y. Uchimura, F. Nagasawa, T. Takeda, H. Kawai, R. Katoono, K. Fujiwara, K. Murakoshi, T. Fukushima, A. Nagaki, J. Yoshida,
  • Journal Title: Chem. Lett. Volume: 43(1), Pages: 85-88
  • Peer Reviewed
• [Journal Article] Electrochromic and unique chiroptical properties of helically deformed tetraarylquinodimethanes generated from less hindered dicationic precursors upon reduction, (2014)
  • Author(s): T. Suzuki, Y. Sakano, T. Iwai, S. Iwashita, Y. Miura, R. Katoono, H. Kawai, K. Fujiwara, Y. Tsuji, T. Fukushima,
  • Journal Title: Pure Appl. Chem Volume: 印刷中 Pages: 印刷中
  • DOI: doi:10.1515/pac-2013-1003
  • Peer Reviewed
• [Journal Article] Cyanoazulene-based Muti-stage Redox Systems Prepared from Vinylcyclopropanecarbonitrile and Cyclopentenone via Divinylcyclopropane-rearrangement Approach, (2014)
  • Author(s): K. Tanino, Y. Yamada, F. Yoshimura, T. Suzuki,
  • Journal Title: Chem. Lett. Volume: 43(5) Pages: 607-608
  • Peer Reviewed
• [Journal Article] Preparation and structure of acenaphthylene-1,2-diyldi(9-acridine) derivatives with a long C=C bond, (2014)
  • Author(s): T. Takeda, Y. Uchimura, H. Kawai, R. Katoono, K. Fujiwara, T. Suzuki,
  • Journal Title: Chem. Commun Volume: 50 Pages: 3924-3927
  • Peer Reviewed
• [Journal Article] Complexation-induced inversion of helicity by an organic guest in a dynamic molecular propeller based on a tristerephtalamide host with a two-layer structure (2014)
  • Author(s): R. Katoono, K. Fujiwara, T. Suzuki
  • Journal Title: Chem. Commun. Volume: 50 Pages: 5438-5440
  • DOI: doi: 10.1039/C4CC00323C
  • Peer Reviewed
• [Journal Article] Electrochiroptical Response in Aqueous Media: 9.10-Dihydrophenanthrene-9,10-diyl Dications with Michlar's Hydrol Blue Chromophores Attached with Oligoethylene Glycol Units, (2014)
  • Author(s): T. Suzuki, K. Hanada, R. Katoono, Y. Ishigaki, S. Higasa, H. Higuchi, H. Kikuchi, K. Fujiwara, H. Yamada, T. Fukushima,
  • Journal Title: Chem. Lett. Volume: 印刷中 Pages: 印刷中
  • DOI: doi:10.1246/cl.140163
  • Peer Reviewed
• [Journal Article] Oxidative Protonolysis of the Expanded Central C-C Bond in a Di(spiroacridan)-type Hexaphenylethane Derivative Accompanied by UV-vis, FL, and CD Spectral Changes, (2014)
  • Author(s): T. Suzuki, Y. Kuroda, K. Wada, Y. Sakano, R. Katoono, K. Fujiwara, F. Kakiuchi, T. Fukushima,
  • Journal Title: Chem. Lett. Volume: 印刷中 Pages: 印刷中
  • DOI: doi:10.1246/cl.140192
  • Peer Reviewed
• [Journal Article] 7,7,8,8-Tetraaryl-o-quinodimethane Stabilized by Dibenzo-annulation: A Helical pi-Electron System that Exhibits Electrochromic and Unique Chiroptical Properties, (2013)
  • Author(s): T. Suzuki, Sakano, T. Iwai, S. Iwashita, Y. Miura, R. Katoono, H. Kawai, K. Fujiwara, Y. Tsuji, T. Fukushima,
  • Journal Title: Chem. Eur. J. Volume: 19(1) Pages: 117-123
  • Peer Reviewed
• [Journal Article] Redox switching of conjugation length using 9,9,10,10-tetraaryl-9,10-dihydrophennanthene as an ON/OFF unit: Preparation, X-ray structure, and redox properties of perfluorobiphenyl derivative and its SNAr reactions to pi-extended analogues, (2013)
  • Author(s): T. Suzuki, H. Tamaoki, R. Katoono, K. Fujiwara, J. Ichikawa, T. Fukushima,
  • Journal Title: Chem. Lett. Volume: 42(7) Pages: 703-705
  • Peer Reviewed
• [Journal Article] Oxidative conversion of tetraaryldihydrodibenzothiepins into elemental sulfur and stable cationic dyes accompanied by dual UV-Vis and CD spectral changes (2013)
  • Author(s): T. Suzuki, Kuroda, H. Tamaoki, S. Higasa, R. Katoono, K. Fujiwara, T. Fukushima, H. Yamada,
  • Journal Title: Chem. Lett. Volume: 42(7) Pages: 706-708
  • Peer Reviewed
• [Journal Article] 5,10-Dihydrobenzo[a]indolo[2,3-c]carbazole: A highly fluorescent disk-shaped electron donor exhibiting dual UV-Vis-NIR and fluorescence spectral changes upon electrolysis (2013)
  • Author(s): T. Suzuki, Y. Tokimizu, Y. Sakano, R. Katoono, K. Fujiwara, S. Naoe, N. Fujii, H. Ohno,
  • Journal Title: Chem. Lett. Volume: 42(9) Pages: 1001-1003
  • Peer Reviewed
• [Journal Article] Preparation, properties, and X-ray structures of bis(10-methyl-9- methyleneacridan)-type electron donors with a thiophene/bithiophene/terthiophene skeleton: Redox switching of thiophene-thienoquinoid structure accompanied by UV-Vis-NIR electrochromic response (2013)
  • Author(s): T. Suzuki, Y. Hoshiyama, K. Wada, Y. Ishigaki, Y. Miura, H. Kawai, R. Katoono, K. Fujiwara, T. Fukushima,
  • Journal Title: Chem. Lett. Volume: 42(9) Pages: 1004-1006
  • Peer Reviewed
• [Journal Article] C3-symmetric chrioptical molecular propeller based on hexakis(phenylethynyl)benzene with a threefold terephthalamide: stereospecific propeller generation through the cooperative transmission of point chiralities on the host and guest upon complexation, (2013)
  • Author(s): R. Katoono, H. Kawai, M. Ohkita, K. Fujiwara, T. Suzuki,
  • Journal Title: Chem. Commun. Volume: 49(88) Pages: 10352-10354
  • Peer Reviewed
• [Journal Article] Time-integrated one-pot synthesis, X-ray structure, and redox properties of electrochromic 1,3-diarylisobenzofurans (2013)
  • Author(s): T. Hamura, R. Nakayama, K. Hanada, Y. Sakano, R. Katoono, K. Fujiwara, T. Suzuki,
  • Journal Title: Chem. Lett. Volume: 42(10), Pages: 1244-1246
  • Peer Reviewed
• [Journal Article] Geometrical Remote Steric Effects in 4,5-Disubsitituted-9,10-dihydrophenanthrenes: Expansion of Prestrained C9-C10 Bond in Di(spiroacridan) Derivatives (2013)
  • Author(s): K. Wada, T. Takeda, H. Kawai, R. Katoono, K. Fujiwara, T. Suzuki,
  • Journal Title: Chem. Lett. Volume: 42(10) Pages: 1194-1196
  • Peer Reviewed
• [Journal Article] Hexaphenylethanes with an Ultralong C-C Bond: Expandability of the C-C Bond in Highly Strained Tetraarylopyracenes, (2013)
  • Author(s): T. Takada, Y. Uchimura, H. Kawai, R. Katoono, K. Fujiwara, T. Suzuki,
  • Journal Title: Chem. Lett. (Highlight Review) Volume: 42(9) Pages: 954-962
  • Peer Reviewed
• [Presentation] Electrochromic and Unique Chiroptical Properties of Helically Deformed Tetraarylquinodimethanes (2013)
  • Author(s): T.Suzuki
  • Organizer: 15th Internatinal Symposium on Novel Aromatic Compounds
  • Place of Presentation: Howard Civil Service International House (Taiwan)
  • Year and Date: 20130727-20130802
  • Invited