World-Record Molecules : The longest C-C bond and hypervalency

• Project/Area Number: 21350022
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Hokkaido University
• Principal Investigator: SUZUKI Takanori 北海道大学, 大学院・理学研究院, 教授 (70202132)
• Co-Investigator(Kenkyū-buntansha): FUJIWARA Kenshu 北海道大学, 大学院・理学研究院, 准教授 (20222268) ; KAWAI Hidetoshi 北海道大学, 大学院・理学研究院, 助教 (50322798)
• Project Period (FY): 2009 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥20,150,000 (Direct Cost: ¥15,500,000、Indirect Cost: ¥4,650,000); Fiscal Year 2011: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000); Fiscal Year 2010: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000); Fiscal Year 2009: ¥15,470,000 (Direct Cost: ¥11,900,000、Indirect Cost: ¥3,570,000)
• Keywords: 構造有機化学 / 物理有機化学 / 共有結合 / 長い結合 / X線構造 / ジラジカル / 超原子価

Research Abstract

Based on our own results for hexaphenylethane derivative studied so far, it has been proposed that the compound with a ultralong C-C bond would be generated as a stable entity when the two unpaired electron are forced to stay in a proximity in the corresponding diradical without isomerization into the closed-shell species through resonance/peri-cyclic reactions. Based on the above concept have been designed a series of tetraarylpyracenes where the longest C-C bond ever [1.791(3)Å] was determined experimentally. The expandability of such prestrained bonds was also uncovered.

Research Products

• [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): T. Suzuki, Y. Uchimura, Y. Ishigaki, T. Takeda, R. Katoono, H. Kawai, K. Fujiwara, A. Nagaki J.Yoshida
  • Journal Title: Chem. Lett Volume: 41(5) Pages: 541-543
  • NAID: 10030619852
  • 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): T. Suzuki, H. Tamaoki, K. Wada, R. Katoono, T. Nehira, K. Fujiwara
  • Journal Title: Chem. Commun Volume: 48 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): H. Sugino, H. Kawai, K. Fujiwara, T. Suzuki
  • Journal Title: Chem. Lett Volume: 41 Pages: 79-81
  • NAID: 10030222573
  • 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): T.Suzuki, ら
  • Journal Title: Chem.Lett. Volume: (印刷中)
  • NAID: 10030619852
  • 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): M. Ohkita, A. Endo, K. Sumiya, H. Nakanotani, T. Suzuki, C. Adachi
  • Journal Title: J. Luminescence Volume: 131 Pages: 1520-1524
  • 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): Y. Ishigaki, T. Suzuki, J. Nishida, A. Nagaki, N. Takabayashi, H. Kawai, K. Fujiwara, J. Yoshida
  • Journal Title: Materials 4 Pages: 1906-1926
  • NAID: 120004996596
  • Peer Reviewed
• [Journal Article] Improved synthesis of C8-C20 segment of pectenotoxin-2 (2011)
  • Author(s): K. Fujiwara, Y. Suzuki, N. Koseki, S. Murata, A. Murai, H. Kawai, T. Suzuki
  • Journal Title: Tetrahedron Lett Volume: 52 Pages: 5589-5592
  • Peer Reviewed
• [Journal Article] 1,4-Diaryl-7,10-dimethoxyquinoxalino[2,3-b]qu inoxalines and their dihydro derivatives : Redox switching of NIR absorption and fluorescence (2011)
  • Author(s): Y. Miura, H. Kawai, K. Fujiwara, T. Suzuki
  • Journal Title: Chem. Lett Volume: 40 Pages: 975-977
  • NAID: 10029522204
  • Peer Reviewed
• [Journal Article] Synthesis of the C22. C37 segment of prorocentin (2011)
  • Author(s): A. Takemura, Y. Katagiri, K. Fujiwara, H. Kawai, T. Suzuki
  • Journal Title: Tetrahedron Lett Volume: 52 Pages: 1222-1224
  • 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): T.Suzuki, ら
  • Journal Title: Materials Volume: 4 Pages: 1906-1926
  • NAID: 120004996596
  • 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 (2011)
  • Author(s): T.Suzuki, ら
  • Journal Title: Chem.Commun. Volume: 48 Pages: 2812-2814
  • Peer Reviewed
• [Journal Article] Model studies for the stereoselective construction of the BC-ring of armatol F based on Ireland-Claisen rearrangement and relay ring-closing metathesis (2010)
  • Author(s): K. Fujiwara, K. Tanaka, Y. Katagiri, H. Kawai, T. Suzuki
  • Journal Title: Tetrahedron Lett Volume: 51 Pages: 45434546-45434546
  • Peer Reviewed
• [Journal Article] Studies toward the total synthesis of armatol F : stereoselective construction of the C6 and C7 stereocenters and formation of the A-ring skeleton (2010)
  • Author(s): K. Fujiwara, Y. Hirose, D. Sato, H. Kawai, T. Suzuki
  • Journal Title: Tetrahedron Lett Volume: 51 Pages: 4263-4266
  • Peer Reviewed
• [Journal Article] Enhancement of transcriptional activity of mutant p53 tumor suppressor protein through stabilization of tetramer formation by calix[6]arene derivatives (2010)
  • Author(s): R. Kamada, W. Yoshino, T. Nomura, Y. Chuman, T. Imagawa, T. Suzuki, K. Sakaguchi
  • Journal Title: Bioorg. Med. Chem. Lett Volume: 20 Pages: 4412-4415
  • 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): T. Suzuki, Y. Miura, T. Nehira, H. Kawai, K. Fujiwara
  • Journal Title: Chem. Lett Volume: 39 Pages: 659-697
  • NAID: 10027182328
  • Peer Reviewed
• [Journal Article] Drastic Change in Racemization Barrier upon Redox Reactions : Novel Chiral-memory Units Based on Dynamic Redox Systems (2010)
  • Author(s): T. Suzuki, K. Wada, Y. Ishigaki, Y. Yoshimoto, E. Ohta, H. Kawai, K. Fujiwara
  • Journal Title: Chem. Commun Volume: 46 Pages: 4100-4102
  • Peer Reviewed
• [Journal Article] Halochromic Chiroptical Response of Novel Bis(9-acridinyl)-type Fluorophores with a Helical pi-Framework (2010)
  • Author(s): T. Nehira, Y. Yoshimoto, K. Wada, H. Kawai, K. Fujiwara, T. Suzuki
  • Journal Title: Chem. Lett Volume: 39 Pages: 165-167
  • NAID: 130004425755
  • Peer Reviewed
• [Journal Article] Intramolecular Triarylmethane-methylium Complex : Generation, Properties and X-ray Structure of C-H Bridged Carbocation (2010)
  • Author(s): T. Suzuki, T. Takeda, Y. Yoshimoto, T. Nagasu, H. Kawai, K. Fujiwara
  • Journal Title: Pure Appl. Chem Volume: 82 Pages: 1033-1044
  • Peer Reviewed
• [Journal Article] Phenanthrene-4,5-diylbis(10-methylacridinium) with a Short C+-C+Contact : Preparation, Molecular Structure, Redox Properties, and Electrochromic Interconversion withDihydropyrene Derivative (2010)
  • Author(s): T. Suzuki, Y. Yoshimoto, K. Wada, T. Takeda, H. Kawai, K. Fujiwara
  • Journal Title: Heterocycles Volume: 80 Pages: 149-155
  • NAID: 40016900091
  • Peer Reviewed
• [Journal Article] Drastic Change in Racemization Barrier upon Redox Reactions : Novel Chiral-memory Units Based on Dynamic Redox Systems (2010)
  • Author(s): T.Suzuki, K.Wada, Y.Ishigaki, Y.Yoshimoto, E.Ohta, H.Kawai, K.Fujiwara
  • Journal Title: Chem.Commun. Volume: 46 Pages: 4100-4102
  • 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 Dihydropyr ene Derivative (2010)
  • Author(s): T.Suzuki, Y.Yoshimoto, K.Wada, T.Takeda, H.Kawai, K.Fujiwara
  • Journal Title: Heterocycles Volume: 80 Pages: 149-155
  • NAID: 40016900091
  • Peer Reviewed
• [Journal Article] Halochromic Chiroptical Response of Novel Bis (9-acridinyl)-type Fluorophores with a Helical pi-Framework (2010)
  • Author(s): T.Nehira, Y.Yoshimoto, K.Wada, H.Kawai, K.Fujiwara, T.Suzuki
  • Journal Title: Chem.Lett.[Editor's Choice] Volume: 39 Pages: 165-167
  • NAID: 130004425755
  • Peer Reviewed
• [Journal Article] Intramolecular Chirality Transfer in trans-5, 6-Diary1-5, 6-dihydro-1, 10-phenanthroline-5, 6-diols : Solvato-and Halochromic Responses by Circular Dichroism (2010)
  • Author(s): T.Suzuki, Y.Miura, T.Nehira, H.Kawai, K.Fujiwara
  • Journal Title: Chem.Lett. Volume: 39 Pages: 695-697
  • Peer Reviewed
• [Journal Article] Intramolecular Triarylmethane-methylium Complex : Generation, Properties and X-ray Structure of C-H Bridged Carbocation (2010)
  • Author(s): T.Suzuki, T.Takeda, Y.Yoshimoto, T.Nagasu, H.Kawai, K.Fujiwara
  • Journal Title: Pure Appl.Chem. Volume: 182 Pages: 1033-1044
  • 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): R. Katoono, H. Kawai, K. Fujiwara, T. Suzuki
  • Journal Title: J. Am. Chem. Soc. Volume: 131 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): T. Suzuki, S. Mikuni, Y. Ishigaki, H. Higuchi, H. Kawai, K. Fujiwara
  • Journal Title: Chem. Lett Volume: 38 Pages: 748-749
  • NAID: 10025124556
  • 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): T. Suzuki, Y. Ishigaki, T. Iwai, H. Kawai, K. Fujiwara, H. Ikeda, Y. Kano, K. Mizuno
  • Journal Title: Chem. Eur. J. Volume: 15 Pages: 9434-9441
  • 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): T. Suzuki, Y. Miura, R. Tamaki, H. Kawai, K. Fujiwara
  • Journal Title: Chem. Lett Volume: 38 Pages: 670-671
  • NAID: 10025123874
  • 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): T. Takeda, H. Kawai, R. Herges, E. Mucke, Y. Sawai, K. Murakoshi, K. Fujiwara, T. Suzuki
  • Journal Title: Tetrahedron Lett (50th anniversary special issue) Volume: 50 Pages: 3693-3697
  • Peer Reviewed
• [Journal Article] Stereoselective construction of an anti-beta-alkoxy ether by Ireland-Claisen rearrangement for medium-ring ether synthesis (2009)
  • Author(s): K. Fujiwara, N. Kawamura, H. Kawai, T. Suzuki
  • Journal Title: Tetrahedron Lett Volume: 50 Pages: 1236-1239
  • Peer Reviewed
• [Journal Article] Intramolecular methylacridan-methylacridinium complexes with a phenanthrene-4,5-diyl or related skeleton : Geometry-properties relationship in isolable C-H bridged carbocations (2009)
  • Author(s): T. Suzuki, Y. Yoshimoto, T. Takeda, H. Kawai, K. Fujiwara
  • Journal Title: Chem. Eur. J. Volume: 15 Pages: 2210-2216
  • 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): T.Takeda, H.Kawai, R.Herges, E.Mucke, Y.Sawai, K.Murakoshi, K.Fujiwara, T.Suzuki
  • Journal Title: Tetrahedron Lett. (50th anniversary special issue) Volume: 50 Pages: 3693-3697
  • Peer Reviewed
• [Journal Article] Intramolecular methylacridan-methylacridinium complexes with a phenanthrene-4, 5-diyl or related skeleton : Geometry-properties relationship in isolable C-H bridged carbocations (2009)
  • Author(s): T.Suzuki, Y.Yoshimoto, T.Takeda, H.Kawai, K.Fujiwara
  • Journal Title: Chem.Eur.J Volume: 15 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): R.Katoono, H.Kawai, K.Fujiwara, T.Suzuki
  • Journal Title: J.Am.Chem.Soc. Volume: 131 Pages: 16896-16904
  • Peer Reviewed
• [Presentation] Advanced Electrochromism Based on Dynamic Redox Systems : Toward the Realization of Unimolecular Memory and Multi-Functional Properties (2011)
  • Author(s): T. Suzuki
  • Organizer: 12th Chitose International Forum on Photonics Science & Technology
  • Place of Presentation: Chitose
  • Year and Date: 2011-10-13
• [Presentation] Advanced Electrochromism Based on Dynamic Redox Systems : Toward the Realization of Unimolecular Memory and Multi-functional Properties (2011)
  • Author(s): T.Suzuki
  • Organizer: 12th Chitose International Forum on Photonics Science & Technology
  • Place of Presentation: 千歳科学技術大学(千歳市)(招待講演)
  • Year and Date: 2011-10-13
• [Presentation] Multi-input-and-Multi-Output Molecular Response Systems Based on Helical pi-Framework (2010)
  • Author(s): T. Suzuki, T. Hehira, H. Kawai, K. Fujiwara
  • Organizer: Pacifichem 2010
  • Place of Presentation: Honolulu, USA ポスター発表
  • Year and Date: 2010-12-16
• [Presentation] Multi-input-and-Multi-Output Molecular Response Systems Based on Novel Redox Pairs with a Helical pi-Framework (2010)
  • Author(s): T. Suzuki, Y. Ishigaki, H. Kawai, K. Fujiwara
  • Organizer: Symposium on Molecular Chirality 2010
  • Place of Presentation: Sapporo
  • Year and Date: 2010-07-11
• [Presentation] Intramolecular Methylacridane-acridinium Complexes : Isolation, Structure, and Reactivities of the C-H Bridged Carbocation (2009)
  • Author(s): T. Suzuki
  • Organizer: 13th International Symposium on Novel Aromatic Compounds
  • Place of Presentation: Luxemburg
  • Year and Date: 2009-07-20
• [Book] Strained Hydrocarbons : Beyond the van'tHoff and Le Bel Hypothesis (2009)
  • Author(s): T. Suzuki, T. Takeda, H. Kawai, K. Fujiwara
  • Publisher: Ultralong C-C bond