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Formation and Properties of Supramolecular Structures based on Indacene Skeleton

Research Project

Project/Area Number 14540484
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionHokkaido University

Principal Investigator

KAWAI Hidetoshi (2003)  Hokkaido Univ., Grad.School of Sci., Instructor, 大学院・理学研究科, 助手 (50322798)

辻 孝 (2002)  北海道大学, 大学院・理学研究科, 教授 (20029482)

Co-Investigator(Kenkyū-buntansha) 河合 英敏  北海道大学, 大学院・理学研究科, 助手 (50322798)
Project Period (FY) 2002 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥4,100,000 (Direct Cost: ¥4,100,000)
Fiscal Year 2003: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 2002: ¥2,800,000 (Direct Cost: ¥2,800,000)
KeywordsSupramolecules / Cage compounds / Macrocycles / Rotaxane / Molecular Recognition / Redox Properties / Hydrogen Bonding / 篭状構造
Research Abstract

The hydrindacene skeleton is constituted of a rigid aromatic ring and flexible five-membered rings. Functionalization by introducing various substituents at the positions along the XYZ axes offers the skeleton the opportunities to construct molecular devices with diverse properties. And, in 2,6-substituted derivatives, two less bulky groups on five-membered rings-are vertically oriented oa molecular plane.
(a)Preparation and properties of functionalized macrocycles.
The preparation and redox properties of the macrocycles containing multiple units of the (Z)-4,8-dimethoxyhydrindacene 1,that are connected at the 2,6-positions by butadiyne groups were studied. The trimer and tetramer exhibit reversible one-wave oxidation process similar to the monomer unit, 2,6-diethynylhydrindacene, while the dimer undergoes a reversible two-stage one-electron oxidation, which can be accounted for by the electronic interaction between the hydrindacene units.
(b)Preparation and properties of macrocycles constructed by reversible imine bonds.
The preparation of macrocycles by the imine-bond formation between (Z)-hydrindacenedialdehyde 2 and various aromatic diamines were studied. When a mixture of 2 and phenylenediamine 3a or 1,5-diaminonaphthalene 3b in CDC13 or C6D6 left at room temperature, aslightlysoluble macrocycles in a ratio of 2:3=2:2was formed predominantly. Thehost-guest properties of the reduced tetraamine macrocycles 3 were also studied.
(c)Construction of rotaxane structure using hydrindacene as the axle molecule.
In (E)-2, two less bulky formyl groups work as connecting parts with two terphenylamine half-rings by forming imine bonds. Then, the intramolecular macrocyclization of the imine derivative gave the precursor of the pseudo-rotaxane. It was revealed that imine bonds of the macrocycle were hydrolyzed under acidic condition, and the axle (E)-2 was dethreaded from macrecycle.

Report

(3 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • Research Products

    (42 results)

All Other

All Publications (42 results)

  • [Publications] M.Ohkita: "Intramolecular Diels-Alder Reaction of Cyclopenta-1,3-diene Derivatives Generated in Situ from 4-(Pent-4-enyl)cyclopent-2-enone Ethylene Ketals"Journal of Chemical Society, Perkin Transaction 1. 3. 366-370 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Tsuji: "Preparation and kinetic stabilization of highly strained paracyclophanes"Bulletin of the Chemical Society of Japan. 75・3. 413-433 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Suzuki: "Electrochiroptical Response of a Hexaarylethane Derivative with a Helical π-Skeleton : Drastic UV-Vis and CD Spectral Changes upon Electrolysis of 4',5'-Dibromodispiro[xanthene-9,9'(9'H,10'H)-phenanthlene-10',9"-xanthene]"Journal of Chemical Society, Perkin Transaction 2. 11. 1937-1942 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Ohkita: "Supramolecular graphyne : a C(sp)-H…N hydrogen-bonded unique network structure of 2,4,6-triethynyl-1,3,5-triazine"Chemical Communications. 24. 3054-3055 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Tsuji: "Functionalization and kinetic stabilization of the [4]paracyclophane system and aromaticity of its extremely bent benzene ring"Journal of the American Chemical Society. 125・4. 951-961 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Suzuki: "Chiral electron donors and acceptors : novel "electrochiroptical" response"Synthetic Metals. 133-134. 357-358 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Suzuki: "Formation of keto-carbeniums from 1,2,2-triarylacenaphthen-1-ols by breaking a long C-C bond : unusual alcohol protonolysis accompanied by formal hydride abstraction"Tetrahedron Letters. 44・32. 6095-6098 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Higuchi: "Electrochiroptical response of 2,2'-(2,2-diarylethenyl)binaphthyl-type electron donors that undergo reversible C-C bond formation/breaking upon two-electron transfer"Journal of Organic Chemistry. 68・17. 6605-6610 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Suzuki: "A novel redox switch for fluorescence : drastic UV-vis and fluorescence spectral changes upon electrolysis of a hexaphenylethane derivative of 10,10'-dimethylbiacridan"Tetrahedron Letters. 44・36. 6837-6840 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Suzuki: "4,7-Bis(dimethylamino)benzimidazoles and twin-type derivatives : reversible two-stage redox system modulated by proton-transfer"Tetrahedron Letters. 44・43. 7881-7884 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Suzuki: "Preparation, Properties and X-ray Structures of 5,5'-Bi(8-aminoquinoxalyl)s : Novel Wurster-type Electron Donors with a Heterobiaryl skeleton"Tetrahedron Letters. 45・2. 329-333 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Suzuki: "Pyrazino-tetracyanonaphthoquinodimethanes : Sterically Deformed Electron Acceptors Affording Zwitterionic Radicals"Tetrahedron. 60・9. 1997-2003 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Higuchi: "Three-way-output Response System by Electric Potential : UV-Vis, CD and Fluorescence Spectral changes upon Electrolysis of the Chiral Ester of Tetracyanoanthraquinodimethane"Tetrahedron Letters. 45・15. 3027-3030 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Kawai: "Positive homotropic allosteric binding of benzenediols in a hydrindacene-based exoditopic receptor : cooperativity in amide hydrogen bonding"Journal of American Chemical Society. 126・16. 5034-5035 (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Kawai: "Peri-interaction between Diarylmethyl and Diarylmethylium Units in 1,8-Disubstituted Naphthalenes : Preference of Localized Structure for the C-H Bridged Carbocation"Tetrahedron Letters. 45(印刷中). (2004)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Ohkita: "Intramolecular Diels-Alder reaction of cyclopenta-1,3-diene derivatives generated in situ from 4-(pent-4-enyl)cyclopent-2-enone ethylene ketals"J.Chem.Soc.Perkin Trans.. 1,(3). 366-370 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Tsuji: "Preparation and kinetic stabilization of highly strained paracyclophanes"Bull.Chem.Soc.Jp.. 75(3). 413-433 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Suzuki: "Electrochiroptical response of a hexaarylethane derivative with a helical π-Skeleton : Drastic UV-Vis and CD spectral changes upon electrolysis of 4',5'-dibromodispiro-[xanthene-9,9'(9'H,10'H)-phenanthrene-10',9''-xanthene]"J.Chem.Soc.Perkin Trans.. 2,(11). 1937-1942 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Ohkita: "Supramolecular graphyne a C(sp)-H【triple bond】N hydrogen-bonded unique network structure of 2,4,6-triethynyl-1,3,5-triazine"Chem.Commun.. (24). 3054-3055 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Tsuji: "Functionalization and kinetic stabilization of the [4]paracyclophane system and aromaticity of its extremely bent benzene ring"J.Am.Chem.Soc.. 125(4). 951-962 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Suzuki: "Formation of keto-carbeniums from 1,2,2-triarylacenaphthen-1-ols by breaking a long C-C bond : unusual alcohol protonolysis accompanied by hydride abstraction"Tetrahedron Lett.. 44(32). 6095-6098 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Suzuki: "Chiral electron donors and acceptors : Novel "electrochiroptical" response"Synth.Met.. 133-134. 357-358 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Higuchi: "Electrochiroptical response of 2,2'-(2,2-diarylethenyl)binaphthyi-type electron donors that undergo reversible C-C bond formation/breaking upon two-electron transfer"J.Org.Chem.. 68(17). 6605-6610 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Suzuki: "A novel redox switch for fluorescence : drastic UV-vis and fluorescence spectral changes upon electrolysis of a hexaphenylethane derivative of 10,10'-dimethylbiacridan"Tetrahedron Lett.. 44(36). 6837-6840 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Suzuki: "4,7-Bis(dimethylamino)benzimidazoles and twin-type derivatives : reversible two-stage redox system modulated by proton-transfer"Tetrahedron Lett.. 44(43). 7881-7884 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Suzuki: "Preparation, properties and X-ray structures of 5,5'-bi(8-aminoquinoxalyl)s : Novel Wurster-type electron donors with a heterobiaryl skeleton"Tetrahedron Lett.. 45(2). 329-333 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Suzuki: "Pyrazino-tetracyanonaphthoquinodimethanes : sterically deformed electron acceptors affording zwitterionic radicals"Tetrahedron. 60(9). 1997-2003 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Higuchi: "Three-way-output response system by electric potential : UV-Vis, CD and fluorescence spectral changes upon electrolysis of the chiral ester of tetracyanoanthraquinodimethane"Tetrahedron Lett.. 45(15). 3027-3030 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Kawai: "Positive homotropic allosteric binding of Benzenediols in a hydrmdacene-based exoditopic Receptor : Cooperativity in amide hydrogen bonding"J.Am.Chem.Soc.. 126(16). 5034-5035 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.Kawai: "Peri-interaction between diarylmethyl and diarylmethylium units in 1,8-disubstituted naphthalenes : Preference of localized structure for the C-H bridged carbocation"Tetrahedron Lett.. 45(-)(in press). (2004)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] T.Suzuki: "Formation of keto-carbeniums from 1,2,2-triarylacenaphthen-1-ols by breaking a long C-C bond : unusual alcohol protonolysis accompanied by formal hydride abstraction"Tetrahedron Letters. 44・32. 6095-6098 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Higuchi: "Electrochiroptical response of 2,2'-(2,2-diarylethenyl)binaphthyl-type electron donors that undergo reversible C-C bond formation/breaking upon two-electron transfer"Journal of Organic Chemistry. 68・17. 6605-6610 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Suzuki: "A novel redox switch for fluorescence : drastic UV-vis and fluorescence spectral changes upon electrolysis of a hexaphenylethane derivative of 10,10'-dimethylbiacridan"Tetrahedron Letters. 44・36. 6837-6840 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Suzuki: "4,7-Bis(dimethylamino)benzimidazoles and twin-type derivatives : reversible two-stage redox system modulated by proton-transfer"Tetrahedron Letters. 44・43. 7881-7884 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Suzuki: "Preparation, properties and X-ray structures of 5,5'-bi(8-aminoquinoxalyl)s : Novel Wurster-type electron donors with a heterobiaryl skeleton"Tetrahedron Letters. 45・2. 329-333 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Suzuki: "Pyrazino-tetracyanonaphthoquinodimethanes : sterically deformed electron acceptors affording zwitterionic radicals"Tetrahedron. 60・9. 1997-2003 (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.Higuchi: "Three-way-output response system by electric potential : UV-Vis, CD and fluorescence spectral changes upon electrolysis of the chiral ester of tetracyanoanthraquinodimethane"Tetrahedron Letters. 45(印刷中). (2004)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Ohkita: "Intramolecular Diels-Alder Reaction of Cyclopenta-1,3-diene Derivatives Generated in situ from 4-(Pent-4-enyl)cyclopent-2-enone Ethylene Ketals"J.Chem.Soc., Perkin Trans.1. 366-370 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Suzuki: "Electrochiroptical Response of a Hexaarylethane Derivative with a Helical π-Skeleton : Drastic UV-Vis and CD Spectral Changes upon Electrolysis"J.Chem.Soc., Perkin Trans.2. 1937-1942 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Tsuji: "Preparation and Kinetic Stabilization of Highly Strained Paracyclophanes"Bill.Chem.Soc.Jpn. 75・3. 415-433 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Ohkita: "Supramolecular Graphyne : a C(sp)-H…N Hydrogen-bonded Unique Network Structure of 2,4,6-Triethyny1-1,3,5-triazine"Chem.Commun.. 3054-3055 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Tsuji: "Functionalization and Kinetic Stabilization of [4]Paracyclophane System and Aromaticity of its Extremely Bent Benzene Ring"J.Am.Chem.Soc.. 125・4. 951-961 (2003)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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