Integrated syntheses of novel dynamic redox systems exhibiting assembled multiple functions

2013 Fiscal Year Final Research Report

• Project Area: Organic Synthesis based on Integration of Chemical Reactions. New Methodologies and New Materials
• Project/Area Number: 21106012
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Hokkaido University
• Principal Investigator: SUZUKI TAKANORI 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: 集積合成 / 酸化還元系 / 応答性分子 / エレクトロクロミズム

Research Abstract

Electrochromism is a representative function of organic redox systems, by which electrochemical input is reversibly transduced into UV-Vis spectral output. Based on our previous studies on "dynamic redox (dyrex)" systems that undergo reversible C-C bond-formation/-cleavage upon electron transfer, we envisaged that the assembled multiple functions would be endowed under the novel molecular design, and such materials could be prepared exclusively only by using newly developed synthetic methods based on integrated reactions. This work can be divided into two parts: [1] studies on NOVEL MATERIALS exhibiting dynamic redox behavior prepared by integrated reactions; and [2] characterization and exploration of organic redox systems newly prepared by NOVEL INTEGRATED REACTIONS. Most of the research results have been published.

Research Products

• [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-methoxyphe nyl)pyracene (2014)
  • Author(s): Suzuki, T.; Uchimura, Y.; Nagasawa, F.; Takeda, T.; Kawai, H.; Katoono, R.; Fujiwara, K.; Murakoshi, K.; Fukushima, T.; Nagaki, A.;Yoshida
  • Journal Title: J. Chem. Lett Volume: 43(1) Pages: 85-88
  • Peer Reviewed
• [Journal Article] Chiral Memory Units Based on Dynamic Redox Systems with a Dibenzoxepinone Skeleton: Drastic Change in Racemization Barrier and Electrochemical Bistability (2014)
  • Author(s): Wada, K.; Chiba, Y.; Takeda, T.; Kawai, H.; Katoono, R.; Fujiwara, K.; Suzuki, T
  • Journal Title: Heterocycles Volume: 88(2) Pages: 945-952
  • Peer Reviewed
• [Journal Article] Cyanoazulene-based Muti-stage Redox Systems Prepared from Vinylcyclopropanecarbonitrile and Cyclopentenone via Divinylcyclopropane-rearrangement Approach (2014)
  • Author(s): Tanino, K.; Yamada, Y.; Yoshimura, F.; Suzuki, T
  • Journal Title: Chem. Lett Volume: 43(5) Pages: 607-609
  • Peer Reviewed
• [Journal Article] Electrochromic and unique chiroptical properties of helically deformed tetraarylquinodimethanes generated from less hindered dicationic precursors upon reduction (2014)
  • Author(s): Suzuki, T.; Sakano, Y.; Iwai, T.; Iwashita, S.; Miura, Y.; Katoono, R.; Kawai, H.; Fujiwara, K.; Tsuji, Y.; Fukushima, T
  • Journal Title: Pure Appl. Chem Volume: (in press)
  • DOI: 10.1515/pac-2013-1003
  • 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): Katoono, R.; Fujiwara, K.; Suzuki, T
  • Journal Title: Chem. Commun Volume: 50(41) Pages: 5438-5440
  • Peer Reviewed
• [Journal Article] Preparation and structure of acenaphthylene-1,2-diyldi(9-acridine) derivatives with a long C=C bond (2014)
  • Author(s): Takeda, T.; Uchimura, Y.; Kawai, H.; Katoono, R.; Fujiwara, K.; Suzuki, T
  • Journal Title: Chem. Commun Volume: 50(30) Pages: 3924-3927
  • 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): Suzuki, T..; Hanada, K.; Katoono, R.; Ishigaki, Y.; Higasa, S.; Higuchi, H.; Kikuchi, H.; Fujiwara, K.; Yamada, H.; T. Fukushima
  • Journal Title: Chem. Lett Volume: (in press)
  • DOI: 10.1246/cl.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): Suzuki, T.; Kuroda, Y.; Wada, K.; Sakano, Y.; Katoono, R.; Fujiwara, K.; Kakiuchi, F.; Fukushima, T
  • Journal Title: Chem. Lett Volume: (in press)
  • DOI: 10.1246/cl.140192
  • Peer Reviewed
• [Journal Article] Wurster's Blue-type Cation Radicals Framed in a 5,10-Dihydrobenzo[a]indolo[2,3-c]carbazole (BIC) Skeleton: Dual Electrochromism with Drastic Changes in UV-Vis-NIR and Fluorescence (2014)
  • Author(s): Suzuki, T.; Sakano, Y.; Tokimizu, Y; Miura, Y;. Katoono, R.; Fujiwara, K.; Yoshioka, N.; Fujii, N.; Ohno, H
  • Journal Title: Chem. Asian J Volume: (in press)
  • DOI: 10.1002/asia.20142394
  • Peer Reviewed
• [Journal Article] Preparation, Redox Properties, and perties, and X-ray Strucures of Electrochromic 11,11,12,12- Tetraarylanthraquinodimethane and Its Bianthraquinodimethane Analogue: Drastic Geometrical Changes upon Interconversion with the Dicationic Dyes (2014)
  • Author(s): Sakano, Y.; Katoono, R.; Fujiwara, K.; Suzuki, T
  • Journal Title: Chem. Lett Volume: (in press)
  • DOI: 10.1246/cl.140393
  • 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): Suzuki, T.; Sakano, Y.; Iwai, T.; Iwashita, S.; Miura, Y.; Katoono, R.; Kawai, Fujiwara, K.; Tsuji, Y.; Fukushima, T
  • Journal Title: Chem. Eur. J Volume: 19(1) Pages: 117-123
  • Peer Reviewed
• [Journal Article] Hexaphenylethanes with an Ultralong C-C Bond: Expandability of the C-C Bond in Highly Strained Tetraarylopyracenes (2013)
  • Author(s): Takada, T.; Uchimura, Y.; Kawai, H.; Katoono, R.; Fujiwara, K.; Suzuki, T
  • Journal Title: Chem. Lett Volume: 42(9) Pages: 954-962
  • 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): Wada, K.; Takeda, T.; Kawai, H.; Katoono, R.; Fujiwara, K.; Suzuki, T
  • Journal Title: Chem. Lett Volume: 42(10) Pages: 1194-1196
  • Peer Reviewed
• [Journal Article] Time-integrated one-pot synthesis, X-ray structure, and redox properties of electrochromic 1,3-diarylisobenzofurans (2013)
  • Author(s): Hamura, T.; Nakayama, R.; Hanada, K.; Sakano, Y.; Katoono, R.; Fujiwara, K.; Suzuki, T
  • Journal Title: Chem. Lett Volume: 42(10) Pages: 1244-1246
  • 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): Katoono, R.; Kawai, H.; Ohkita, M.; Fujiwara, K.; Suzuki, T
  • Journal Title: Chem. Commun Volume: 49(88) Pages: 10352-10354
  • 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): Suzuki, T.; Hoshiyama, Y.; Wada, K.; Ishigaki, Y.; Miura,Y.; Kawai, H.; Katoono, R.; Fujiwara, K.; Fukushima, T
  • Journal Title: Chem. Lett Volume: 42(9) Pages: 1004-1006
  • 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): Suzuki, T.; Tokimizu, Y.; Sakano, Y.; Katoono, R.; Fujiwara, K.; Naoe, S.; Fujii, N.; Ohno, H
  • Journal Title: Chem. Lett Volume: 42(9) Pages: 1001-1003
  • 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): Suzuki, T.; Kuroda, T.; Tamaoki, H.; Higasa, S.; Katoono, R.; Fujiwara, K.; Fukushima, T.; Yamada, H
  • Journal Title: Chem. Lett Volume: 42(7) Pages: 706-708
  • 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): Suzuki, T.; Tamaoki, H.; Katoono, R.; Fujiwara, K.; Ichikawa, J.; Fukushima, T.
  • Journal Title: Chem. Lett Volume: 42(7) Pages: 703-705
  • Peer Reviewed
• [Journal Article] Hydrindacene-based acetylenic macrocycles with horizontally and vertically ordered functionality arrays (2013)
  • Author(s): Kawai, H.; Utamura, T.; Motoi, E.; Takahashi, T.; Sugino, H.; Tamura, M.; Ohkita, M.; Fujiwara, K.; Saito, T.; Tsuji, T.; Suzuki, T
  • Journal Title: Chem. Eur. J Volume: 19(14) Pages: 4513-4524
  • Peer Reviewed
• [Journal Article] Induced Preference for Axial Chirality in a Triarylmethylium o,o-Dimer upon Complexation with Natural gamma-Cyclodextrin: Strong ECD Signaling and Fixation of Supramolecular Chirality to Molecular Chirality (2012)
  • Author(s): Suzuki, T.; Tamaoki, H.; Wada, K.; Katoono, R.; Nehira, T.; Fujiwara, K
  • Journal Title: Chem. Commun Volume: 48 (22) Pages: 2812-2814
  • Peer Reviewed
• [Journal Article] Molecular Gyroscope with a trans-cyclohexane-1,4-diimine rotor unit: Isolation and characterization of a geometrical isomer as a formal intermediate of hindered rotation (2012)
  • Author(s): Sugino, H.; Kawai, H.; Fujiwara, K.; Suzuki, T
  • Journal Title: Chem. Lett. Volume: 41 (1) Pages: 79-81
  • Peer Reviewed
• [Journal Article] Effects of Axle-Core, Macrocycle, and Side-Station Structures on the Threading and Hydrolysis Processes of Imine-Bridged Rotaxanes (2012)
  • Author(s): Sugino, H.; Kawai, H.; Umehara, T.; Fujiwara, K.; Suzuki, T
  • Journal Title: Chem. Eur. J Volume: 18(43) Pages: 13722-13733
  • Peer Reviewed
• [Journal Article] Non-additive Substituent Effects on Expanding Prestrained C-C Bond in Crystal: X-ray Analyses on Unsymmetrically Substituted Tetraarylpyracenes Prepared by a Flow Microreactor Method (2012)
  • Author(s): Suzuki, T.; Uchimura, Y.; Ishigaki, Y.; Takeda, T.; Katoono, R.; Kawai, H.; Fujiwara, Nagaki, A.; Yoshida
  • Journal Title: J. Chem. Lett Volume: 41(5) Pages: 541-543
  • Peer Reviewed
• [Journal Article] Stable neutral radicals based on the polyazaacene skeleton that exhibit high electrochemical amphotericity (2012)
  • Author(s): Miura, Y.; Chiba, H.; Katoono, R.; Kawai, Fujiwara, K.; Suzuki, S.; Okada, K.; Suzuki, T
  • Journal Title: Tetrahedron Lett Volume: 53(48) Pages: 6561-6564
  • Peer Reviewed
• [Journal Article] Hysteretic Tricolor Electrochromic Systems Based on the Dynamic Redox Properties of Unsymmetrically Substituted Dihydrophenanthrenes and Biphenyl-2,2'-Diyl Dications: Efficient Precursor Synthesis by a Flow Microreactor Method (2011)
  • Author(s): Ishigaki, Y.; Suzuki, T.; Nishida, J.; Nagaki, A.; Takabayashi, N.; Kawai, H; .Fujiwara, K.; Yoshida, J
  • Journal Title: Materials Volume: 4 (11) Pages: 1906-1926.
  • Peer Reviewed
• [Journal Article] 1,4-Diaryl-7,10-dimethoxyquinoxalino[2,3-b]q uinoxalines and their dihydro derivatives: Redox switching of NIR absorption and fluorescence (2011)
  • Author(s): Miura, Y.; Kawai, H.; Fujiwara, K.; Suzuki, T
  • Journal Title: Chem. Lett Volume: 40 (*9) Pages: 975-957
  • Peer Reviewed
• [Journal Article] Photophysical characterization of 4,4'-bis(N-carbazolyl)tolan derivatives and their application in organic light emitting diodos (2011)
  • Author(s): Ohkita, M.; Endo, A.; Sumiya, K.; Nakanotani, H.; Suzuki, T.; Adachi, C. J
  • Journal Title: Luminescence Volume: 131 (7) Pages: 1520-1524
  • Peer Reviewed
• [Journal Article] イミン架橋によって環の動的挙動を制御する主鎖型オリゴロタキサンの構築とそのスイッチング特性 (2011)
  • Author(s): 杉野寛佳,河合英敏,藤原憲秀,鈴木孝紀
  • Journal Title: 高分子論文集 Volume: 68 (12) Pages: 795-803
  • Peer Reviewed
• [Journal Article] Drastic Change in Racemization Barrier upon Redox Reactions: Novel Chiral-memory Units Based on Dynamic Redox Systems (2010)
  • Author(s): Suzuki, T.; Wada, K.; Ishigaki, Y.; Yoshimoto, Y.; Ohta, E.; Kawai, H.; Fujiwara, K
  • Journal Title: Chem. Commun Volume: 46(23) Pages: 4100-4102
  • Peer Reviewed
• [Journal Article] Intramolecular Triarylmethane-methylium Complex: Generation, Properties and X-ray Structure of C-H Bridged Carbocation (2010)
  • Author(s): Suzuki, T.; Takeda, T.; Yoshimoto, Y.; Nagasu, T.; Kawai, H.; Fujiwara, K
  • Journal Title: Pure Appl. Chem Volume: 82(4) Pages: 1033-1044
  • Peer Reviewed
• [Journal Article] Intramolecular Chirality Transfer in trans-5,6-Diaryl-5,6-dihydro-1,10-phenanthroline-5,6-diols: Solvato- and Halochromic Responses by Circular Dichroism (2010)
  • Author(s): Suzuki, T.; Miura, Y.; Nehira, T.; Kawai, H.; Fujiwara, K
  • Journal Title: Chem. Lett Volume: 39(7) Pages: 695-697
  • Peer Reviewed
• [Journal Article] Halochromic Chiroptical Response of Novel Bis(9-acridinyl)-type Fluorophores with a Helical pi-Framework (2010)
  • Author(s): Nehira, T.; Yoshimoto, Y.; Wada, K.; Kawai, H.; Fujiwara, K.; Suzuki, T
  • Journal Title: Chem. Lett Volume: 39(3) Pages: 165-167
  • Peer Reviewed
• [Journal Article] Phenanthrene-4,5-diylbis(10-methylacridinium) with a Short C^+ - - C^+ Contact: Preparation, Molecular Structure, Redox Properties, and Electrochromic Interconversion with Dihydropyrene Derivative (2010)
  • Author(s): Suzuki, T.; Yoshimoto, Y.; Wada, K.; Takeda, T.; Kawai, H.; Fujiwara, K
  • Journal Title: Heterocycles Volume: 80(1) Pages: 149-155
  • Peer Reviewed
• [Journal Article] Multi-input-Multi-output Molecular Response System Based on Dynamic Redox Behavior of 3,3,4,4-Tetraaryldihydro[5]helicene Derivatives: Reversible Formation/Destruction of Chiral Fluorophore and Modulation of Chiroptical Properties by Solvent Polarity (2009)
  • Author(s): Suzuki, T.; Ishigaki, Y.; Iwai, T.; Kawai, H.; Fujiwara, K. Ikeda, H.; Kano, Y.; Mizuno, K
  • Journal Title: Chem. Eur. J Volume: 15(37) Pages: 9434-9441
  • Peer Reviewed
• [Journal Article] Intramolecular methylacridanmethylacridinium complexes with a phenanthrene-4,5-diyl or related skeleton: Geometry-properties relationship in isolable C-H bridged carbocations (2009)
  • Author(s): Suzuki, T.; Yoshimoto, Y.; Takeda, T.; Kawai, H.; Fujiwara, K
  • Journal Title: Chem. Eur. J Volume: 15(9) Pages: 2210-2216
  • Peer Reviewed
• [Journal Article] Dynamic Molecular Propeller: Supramolecular Chirality Sensing by Enhanced Chiroptical Response through the Transmission of Point Chirality to Mobile Helicity (2009)
  • Author(s): Katoono, R.; Kawai, H.; Fujiwara, K.; Suzuki, T
  • Journal Title: J. Am. Chem. Soc Volume: 131(46) Pages: 16896-16904
  • Peer Reviewed
• [Journal Article] 4,5-Bis(diarylmethylene)-1,3-dithiole: A Novel Helical Electron Donor Exhibiting Electrochromic Behavior (2009)
  • Author(s): Suzuki, T.; Mikuni, S.; Ishigaki, Y.; Higuchi, H.; Kawai, H.; Fujiwara, K
  • Journal Title: Chem. Lett Volume: 38(7) Pages: 748-749
  • Peer Reviewed
• [Journal Article] Preparation and X-ray Structures of trans-5,6-Diaryl-5,6-dihydro-1,10- phenanthroline-5,6-diols: Formation of Supramolecular Rod by Hydrogen Bonds (2009)
  • Author(s): Suzuki, T.; Miura, Y.; Tamaki, R.; Kawai, H.; Fujiwara, K
  • Journal Title: Chem. Lett Volume: 38(7) Pages: 670-671
  • Peer Reviewed
• [Journal Article] Negligible diradical character for the ultralong C-C bond in 1,1,2,2-tetraarylpyracene derivatives at room temperature (2009)
  • Author(s): Takeda, T.; Kawai, Herges, R.; Mucke, E.; Sawai, Y.; Murakoshi, K.; H.; Fujiwara, K.; Suzuki, T
  • Journal Title: Tetrahedron Lett Volume: 50(26)(50th anniversary special issue) Pages: 3693-3697
  • Peer Reviewed
• [Presentation] Toward the World-Record Compound with the Longest C-C Bond: X-ray Analyses on Unsymmetrically Substituted Tetraarylpyracenes Prepared by a Flow Microreactor Method (2013)
  • Author(s): Suzuki, T
  • Organizer: The 8 th International Symposium on Integrated Synthesis (ISIS-8)
  • Place of Presentation: Todaiji Temple Cultural Center, Nara
  • Year and Date: 20131129-1201
  • Invited
• [Presentation] Electrochromic and Unique Chiroptical Properties of Helically Deformed Tetraarylquinodimethanes (2013)
  • Author(s): Suzuki, T
  • Organizer: The 15 th International Symposium on Novel Aromatic Compounds (ISNA-15)
  • Place of Presentation: Howard Civil Service International House, Taiwan
  • Year and Date: 20130728-0802
  • Invited
• [Presentation] Intramolecular Triarylmethane-methylium Complex: Generation, Properties and X-ray Structure of a C-H Bridged Carbocations (2012)
  • Author(s): Suzuki, T
  • Organizer: 2012 Hokkaido University & Peking University Joint Symposium on Organic and Organometallic Chemistry
  • Place of Presentation: Hokkaido Univ., Sapporo
  • Year and Date: 2012-07-17
  • Invited
• [Presentation] Advanced Electrochromism Based on Dynamic Redox Systems: Toward the Realization of Unimolecular Memory and Multi-functional Properties (2011)
  • Author(s): Suzuki, T
  • Organizer: 12th Chitose International Forum on Photonics Science & Technology (CIF12)
  • Place of Presentation: Chitose Institute of Science and Technology, Chitose
  • Year and Date: 2011-10-13
  • Invited
• [Presentation] Intramolecular Methylacridan-acridinium Complexes: Isolation, Structure, and Reactivities of the C--H Bridged Carbocations (2009)
  • Author(s): Suzuki, T. Yoshimoto, Y.; Takeda, T.; Kawai, H.; Fujiwara, K
  • Organizer: The 13 th International Symposium on Novel Aromatic Compounds (ISNA-13)
  • Place of Presentation: The Hemicycle Conference Center, Luxembourg
  • Year and Date: 20090719-24
  • Invited
• [Presentation] Molecular Response Systems based on Hexaphenylethanes: Toward the Realization of Unimolecular Memory and Multi-functional Properties (2009)
  • Author(s): Suzuki, T
  • Organizer: The Second International Symposium on Interdisciplinary Materials and Science (ISIMS-2)
  • Place of Presentation: University of Tsukuba, Tsukuba
  • Year and Date: 20090309-10
  • Invited
• [Presentation] エレクトロクロミズム系の新展開:双安定性と多重出入力機能 (2009)
  • Author(s): 鈴木 孝紀
  • Organizer: 大阪大学大学院基礎工学研究院特別講演会
  • Place of Presentation: 大阪大学、豊中市
  • Year and Date: 2009-10-29
  • Invited
• [Presentation] エレクトロクロミズム系の新展開:双安定性と多重出入力機能(英語) (2009)
  • Author(s): 鈴木 孝紀
  • Organizer: 理化学研究所特別講演会
  • Place of Presentation: 理化学研究所, 和光市
  • Year and Date: 2009-01-14
  • Invited