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2002 Fiscal Year Final Research Report Summary

Synthesis and Functional Organization of Multiply N-Confused Porphyrins

Research Project

Project/Area Number 13440189
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKyushu University (2002)
Kyoto University (2001)

Principal Investigator

FURUTA Hiroyuki  Kyushu University, Faculty of Engineering, Professor, 工学研究院, 教授 (40244157)

Project Period (FY) 2001 – 2002
KeywordsPorphyrin / N-Confused porphyrin / Porphyrin Isomer / Metal Complex / Calixphyrin / Expanded Porphyrin / Hexphyrin / Aromaticity
Research Abstract

The total electronic energy and nucleus-independent chemical shift (NICS) of 95 isomers of N-confused porphyrin (NCP) have been calculated by density functional theory (DFT) method. The aromatic nature and the stability were not directly related. The introduction of confusion decreases the stability ca. 18 kcal/mol per one confusion. The results were partially supported by the actual synthesis of cis-doubly N-confused porphyrin (N2CP). Furthermore, a different type of porphyrinoids, such as corrorin, oxyindolophyrin, and tripyrrinone, were obtained in the reactions of N2CP and NCP metal complexation. Electrochemistry and photochemistry of N2CP metal complexes were investigated and the potentiality for the use in water splitting and photodynamic therapy (PDT) were suggested.
On the other hand, a series of expanded porphyrins including, pentaphyrin, hexaphyrin, octaphyrins, and nonaphyrins, were synthesized and the structures were determined by the X-ray single crystal analyses. The normal type of meso-aryl substituted expanded porphyrins were non-planar but the doubly N-confused hexaphyrins were fond planar and could complex bis metal ions in the cavity maintaining the aromaticity.
The inner and outer metal coordination were found more general for the NCP. By using Pd(II) and Pt(II), unique double-decker type face-to-face dimers and the linear linked dimers were synthesized, respectively. When Zn(II) and Cd(II) were used, a new type of metal bridged dimers were formed. A versatile mode of NCP metal coordination were explicitly elucidated and opened the way for the metal assisted supramolecular assembly.

  • Research Products

    (62 results)

All Other

All Publications (62 results)

  • [Publications] Shin, J.-Y.: "N-Fused Pentaphyrins"Angew.Chem., Int.Ed.. 40. 619-621 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Araki, K.: "Acid-Base and Spectroelectrochemical Properties of Doubly N-Confused Porphyrins"Inorg.Chem.. 40. 2020-2025 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Pushpan, S.K.: "N-Confused Expanded Porphyrins : First Example of a Modified Sapphyrin with an Inverted N-Confused Pyrrole Ring"J.Am.Chem.Soc.. 123. 5138-5139 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Furuta, H.: "Metal Complexes of N-Confused Calix[4]phyrin Derivative-The First X-ray Structure of Organometallic Compound of Divalent Copper"Angew.Chem., Int.Ed.. 40. 2323-2325 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Furuta, H.: "NH Tautomerism of N-Confused porphyrin"J.Am.Chem.Soc.. 123. 6207-6208 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Furuta, H.: "Metal Complexes of N-Confused Calix[4]phyrin Derivative-The First X-ray Structure of Organometallic Compound of Divalent Copper"J.Am.Chem.Soc.. 123. 6435-6436 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Shin, J.-Y.: "Meso-Aryl Substituted Expanded Porphyrins"J.Am.Chem.Soc.. 123. 7190-7191 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Furuta, H: "Theoretical Study of Stability, Structures, and Aromaticity of Multiply N-Confused Porphyrins"J.Org.Chem.. 66. 8563-8572 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Alagar, S.: "The First bis-Rh(I) Complex of N-Confused Porphyrin"Chem.Commun.. 1666-1667 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nakano, A.: "Directly Linked Dehydropurpurin -Porphyrin Dyads from Ag(I)-promoted Oxidation of meso-Phenylethynyl Substituted Zinc(II) Porphyrins"Chem.Commun.. 1920-1921 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Tsuda, A.: "Syntheses, Structural Characterizations, and Optical and Electrochemical Properties of Directly Fused Diporhyrins"J.Am.Chem.Soc.. 123. 10304-10321 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Furuta, H.: "Regioselective Oxidative Liberation of Aryl-Substituted Tripyrrinone Metal Complexes from N-Confused Porphyrin"Org.Lett.. 4. 181-184 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Sessler, J.L.: "Quinoxaline-oligopyrroles : Improved Pyrrole-based Anion Receptors"Chem.Commun.. 862-863 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Furuta, H: "Flexible Inner and Outer Coordination of Zn(II) N-Confused Porphyrin Complex"J.Am.Chem.Soc.. 124. 5622-5623 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Furuta, H: "Confusion, Inversion, and Creation -A New Spring from Porphyrin Chemistry"Chem.Commun.. 1795-1804 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Shinmori, H: "Effective Face-to-face Dimerization of a Crown Ether Appended N-Confused porphyrins"Tetrahedron Lett.. 43. 4881-4884 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Takase, M.: "Efficient Synthesis of Benzene-Centered Cyclic Porphyrin Hexamers"Tetrahedron Lett.. 43. 5157-5159 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Sessler, J.L.: "Quinoxaline-Bridged Porphyrinoids"J.Am.Chem.Soc.. 124. 13474-13479 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Shimizu, S.: "Perfluorinated meso-Aryl Expanded Porphyrins"Angew.Chem., Int.Ed.. 42. 78-82 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Furuta, H.: "Crystal Structures of Palladium(II) and Copper(II) Complexes of meso-Phenyl Tripyrrinone"Inorg.Chem.Commun.. 6. 162-164 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Furuta, H: "Zinc Complex of N-confused Calix[4]phyrin"Inorg.Chem.Commun.. 6. 398-401 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Alagar, S.: "Doubly N-Confused Hexaphyrin : A Novel Aromatic Expanded Porphyrin that Complexes Bis-Metals in the Core"J.Am.Chem.Soc.. 125. 878-879 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Araki, K.: "Doubly N-Confused Porphyrins as Efficient Sensitizers for Singlet Oxygen Generation"Chem.Lett.. 32. 244-245 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Taniguchi, R.: "Ring Size Selective Synthesis of meso-Aryl Expanded Porphyrins"Tetrahedron Lett.. 44. 2505-2507 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Furuta, H.: "Facile Formation of N-Confused Porphyrin Dimers by Pt(II) Coordination to Outer-Nitrogens"Angew.Chem., Int.Ed.. 42. 2186-2188 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Maeda, H: "2-Allenylbenzotriazole"Acta Crysatllogr. C.. 59. o338-o339 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Liu, J.-C.: "Modulation of Axial Coordination in N-Confused Porphyrin-Antimony(V) Dibromide Complex by Proton Stimulus"Chem.Commun.. (印刷中). (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Furuta, H.: "Chemistry of N-confused Porphyrin : A Novel Porphyrin Isomer"J. Oleo Sci.. 3. 77-82 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Maeda, H.: "1D Hydrogen Bonding 1-D Chain Network of Cis-Doubly N-Confused Porphyrins"Supramolecular Chemistry. 15(印刷中). (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Meda, H.: "N-Confused Porphyrin Bearing meso-Perfluorophenyl Group : A Potential Agent that Forms Stable Squareplanar Complexes with Cu(II) and Ag(III)"Org.Lett. 5. 1293-1296 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Furuta, H.: "Synthesis and Structures of N-Confused 5, 20-Diphenylporphy rin and Ag(III) Complex"Org.Lett. 5. 1427-1430 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Shin, J. -Y.: "N-Fused Pentaphyrins"Angew Chem. Int. Ed.. 40. 619-621 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Araki, K.: "Acid-Base and Spectroelectrochemical Properties of Doubly N-Confused Porphyrins"Inorg. Chem.. 40. 2020-2025 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Pushpan, S. K.: "N-Confused Expanded Porphyrins : First Example of a Modified Sapphyrin with an Inverted N-Confused Pyrrole Ring"J. Am. Chem.. 123. 5138-5139 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Furuta, H.: "Metal Complexes of N-Confused Calix[4]phyrin Derivative- The First X-ray Structure of Organometallic Compound of Divalent Copper"Angew. Chem. Int. Ed.. 40. 2323-2325 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Furuta, H.: "NH Tautomerism of N-Confused porphyrin"J. Am. Chem. Soc.. 123. 6207-6208 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Furuta, H.: "Oxyindolophyrin : A Novel Fluoride Receptor Derived from N-Confused Corrole Isomer"J. Am. Chem. Soc.. 123. 6435-6436 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Shin, J. -Y.: "Meso-Aryl Substituted Expanded Porpyrins"J. Am. Chem. Soc.. 123. 7190-7191 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Furuta, H.: "Theoretical Study of Stability, Structures, and Aromaticity of Multiply N-Confused Porphyrins"J. Org. Chem.. 66. 8563-8572 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Alagar, S.: "The Firsr bis-Rh(I) Complex of N-Confused Porphyrin"Chem. Commun.. 1666-1667 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nakano, A.: "Directly Linked Dehydropurpurin - Porphyrin Dyads from Ag(I)-promoted Oxidation of meso-Phenylethynyl Substituted Zinc(II) Porphyrins"Chem. Commun.. 1920-1921 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Tsuda, A.: "Syntheses, Structural Characterizations, and Optical and Electrochemical Properties of Directly Fused Diporphyrins"J. Am. Chem. Soc.. 123. 10304-10321 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Furuta, H.: "Regioselective Oxidative Liberation of Aryl-Substituted Tripyrrinone Metal Complexes from N-Confused Porphyrin"Org. Lett.. 4. 181-184 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Sessler, J. L.: "Quinoxaline-oligopyrroles : Improved Pyrrole-based Anion Receptors"Chem. Commun.. 862-863 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Furuta, H.: "Flexible Inner and Outer Coordination of Zn(II) N- Confused Porphyrin Complex"J. Am. Chem. Soc.. 124. 5622-5623 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Furuta, H.: "Confusion, Inversion, and Creation - A New Spring from Porphyrin Chemistry"Chem. Commun.. 1795-1804 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Shinmori, H.: "Effective Face-to-face Dimerization of A Crown Ether Appended N-Confused porphyrins"Tetrahedron Lett.. 43. 4881-4884 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Takase, M.: "Efficient Synthesis of Benzene-Centered Cyclic Porphyrin Hexamers"Tetrahedron Lett.. 43. 5157-5159 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Sessler, J. L.: "Quinoxaline-Bridged Porphyrinoids"J. Am. Chem. Soc.. 124. 13474-13479 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Shimizu, S.: "Perfluorinated meso-Aryl Expanded Porphyrins"Angew. Chem. Int. Ed.. 42. 78-82 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Furuta, H.: "Crystal Structures of Palladium(II) and Copper(II) Complexes of meso-Phenyl Tripyrrinone"Inorg. Chem. Commun.. 6. 162-164 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Furuta, H.: "Zinc Complex of N-confused Calix[4]phyrin"Inorg. Chem. Commun.. 6. 398-401 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Alagar, S.: "Doubly N-Confused Hexaphyrin : A Novel Aromatic Expanded Porphyrin that Complexes Bis-Metals in the Core"J. Am. Chem. Soc.. 125. 878-879 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Araki, K.: "Doubly N-Confused Porphyrins as Efficient Sensitizers for Singlet Oxygen Generation"Chem. Lett.. 32. 244-245 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Taniguchi, R.: "Ring Size Selective Synthesis of meso-Aryl Expanded Porphyrins"Tetrahedron Lett.. 44. 2505-2507 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Furuta, H.: "Facile Formation of N-Confused Porphyrin Dimers by Pt(II) Coordination to Outer-Nitrogens"Angew. Chem. Int. Ed.. 42. 2186-2188 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Maeda, H.: "N-Confused Porphyrin Bearing meso-Perfluorophenyl Groups : A Potential Agent that Forms Stable Squareplanar Complexes with Cu(II) and Ag(III)"Org. Lett.. 5. 1293-1296 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Furuta, H.: "Synthesis and Structures of N-Confused 5,20- Diphenylporphyrin and Ag(III) Complex"Org. Lett.. 5. 1427-1430 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Maeda, H.: "2-Allenylbenzotriazole"Acta Crysatllogr. C. 59. o338-o339 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Liu, J. -C.: "Modulation of Axial Coordination in N-Confused Porphyrin-Antimony(V) Dibromide Complex by Proton Stimulus"Chem. Commun.. in press.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Furuta, H.: "Chemistry of N-confused Porphyrin : A Novel Porphyrin Isomer"J. Oleo Sci.. 3. 77-82 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Maeda, H.: "Hydrogen Bonding 1-D Chain Network of Cis-Doubly N- Confused Porphyrins"Supramolecular Chemistry. in press.

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2004-04-14  

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