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2001 Fiscal Year Final Research Report Summary

Development of novel chromophores whose magnetic properties are controlled by photoexcitation

Research Project

Project/Area Number 11440192
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionTohoku University

Principal Investigator

KOBAYASHI Nagao  Graduate School of Science, Tohoku University, Professor, 大学院・理学研究科, 教授 (60124575)

Co-Investigator(Kenkyū-buntansha) ISHII Kazuyuki  Graduate School of Science, Tohoku University, Research Associate, 大学院・理学研究科, 助手 (20282022)
Project Period (FY) 1999 – 2001
KeywordsPhotomagnetism / Excited multiplet state / Porphyrin / Phthalocyanine / Nitroxide radical
Research Abstract

In order to realize novel chromophores whose magnetic properties are controlled by photoexcitation, several chromophores linked to nitroxide radicals have been synthesized, and the magnetic properties after photoexcitation have been investigated. Followings are clarified.
1. The interactions between the chromophores in the excited triplet state and nitroxide radical in the doublet ground state are systematically changed by synthesizing porphyrin or phthalocyanine complexes coordinated to nitroxide radical. The relationship between the bond number, distance, electron exchange interaction, lifetime, and electron spin polarization are clarified.
2. Phthalocyaninatosilicons covalently linked to two nitroxide radicals have been investigated. In several microseconds, the magnetic properties in the ground state are controlled by photoexcitation, such as (thermal equillibrium)→(singlet)→(triplet)→(thermal equillibrium). These spin dynamics is reasonably interpreted by analyzing transient absorption and time-resolved EPR results.
3. Light illumination effects on the magnetic properties of the crystal of phthalocyanine linked to one nitroxide radical have been studied. By the photoexcitation of Pc chromophore, the β spin of the nitroxide radical is efficiently changed to the α spin. That is, we have succeeded in controlling the magnetic properties of the paramagnetic crystal by photoexcitation.

  • Research Products

    (78 results)

All Other

All Publications (78 results)

  • [Publications] Kazuyuki Ishii: "Experimental Evidence for a Selection Rule of Intersystem Crossing to the Excited Quartet States : Metallophthalocyanines Coordinated by 4-Amino-TEMPO"J. Phys. Chem. A. 103. 6060-6062 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hideya Miwa: "A Novel Phthalocyanine Isomer : A Dinaphthophthalocyanine with C2v Symmetry"Chem. Lett.. 1303-1304 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hideya Miwa: "Synthesis, Spectroscopy, Electrochemistry, and Mesomorphism of Triple-Decker Porphyrins Consisting of Two Cerium Ions and Three 5,15-Diarylporphyrins"Bull. Chem. Soc. Jpn.. 72. 2719-2728 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagao Kobayashi: "Substituent-Induced Circular Dichroism in Phthalocyanines"J.Am. Chem. Soc.. 121. 12018-12028 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagao Kobayashi: "Phthalocyanines"Current Opinion in Solid State and Material Science. 4. 345-353 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 小林長夫: "フタロシアニン系巨大分子-多方面で実用化されている巨大分子"化学と工業. 52. 968-971 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagao Kobayashi: "A mutually perpendicular phthalocyanine pentamer obtained by a one-step reaction"Chem. Commun.. 103. 1855-1856 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] V.N.Nemykin: "Low Symmetrical Phthalocyanines Having Spectroscopic and Electrochemical Properties Characteristic of Unexpected Accidental S1 state Degeneracy and Non-Planar Distortion"Chem. Lett.. 184-185 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] V.N.Nemykin: "The Solid Phase, Room-Temperature Synthesis of Metal-free and Metallophthalo-cyanines, Particularly of 2,3,9,10,16,17,23,24-Octacyanophthalocyanines"Chem. Lett.. 546-547 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] V.N.Nemykin: "Diels-Alder Reaction of Tribenzo[b, g, f]porphyrazine as a New Path for Porphyrazine Core Modification"Chem. Lett.. 1236-1237 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuyuki Ishii: "The excited multiplet states of metalloporphyrins and metallophthalocyanines coordinated or linked to nitroxide radicals"Coord. Chem. Rev.. 198. 231-250 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuyuki Ishii: "Time-Resolved Electron Spin Resonance of Gallium and Germanium Porphyrins in the Excited Triplet State"Inorg. Chem.. 39. 468-472 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagao Kobayashi: "Symmetry-Lowering of the Phthalocyanine Chromophore by a C2 type Axial Ligand"Inorg. Chem.. 39. 2256-2257 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagao Kobayashi: "Band Deconvolution Analysis of the Absorption and Magnetic Circular Dichroism Spectral Data of a Planar Phthalocyanine Dimer"Inorg. Chem.. 39. 3632-3637 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagao Kobayashi: "Theoretical interpretation of spectroscopic data"J. Porphyrins Phthalocyanines. 4. 377-379 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] V.N.Nemykin: "Synthesis and some spectroscopic properties of tetra-2,3-pyridinoporphyrazinatosilicon involving bulky axial ligands"J. Porphyrins Phthalocyanines. 4. 538-543 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] V.N.Nemykin: "Synthesis and spectroscopic properties of new phthalocyanine complexes with potentially combined photodynamic activity and cytotoxicity for photodynamic therapy"J. Porphyrins Phthalocyanines. 4. 551-554 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] V.N.Nemykin: "First direct calculation of the partial quadrupole splitting of ligands for the prediction of Mossbauer spectra parameter in low spin iron(II) complexes"Mendeleev Comm.. 2. 43-82 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 石井和之: "ニトロキシドラジカルと結合したポルフィリン錯体の光励起多重項状態 -励起多重項状態の評価と磁気的性質の光制御に関する新規概念-"化学と工業. 54. 144-147 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagao Kobayashi: "A Seven-Membered Carbon-Ring-Fused Phthalocyanine Analogue in which the π System Change during Dehydrogenation/Hydrogenation Cycles"Angew. Chem. Int. ed.. 40. 1300-1303 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagao Kobayashi: "A Novel Hemiporphyrazine Comprising Three Isoindolediimine and Three Thiadiazole Units"Angew. Chem. Int. ed.. 40. 2710-2712 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] V.N.Nemykin: "A tetraazaporphyrin with an intense, broad near-IR band"Chem. Commun.. 165-166 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuyuki Ishii: "Relationship between the Excited Multiplet EPR and Phosphorescence Lifetime in the Excited Triplet Octaethylporphinatozinc Coordinated by One TEMPO Radical"Chem. Lett.. 482-483 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Fumio Furuya: "Synthesis, Structure, and Crystal Characterization of Sandwich-type (2,3-Naphthalocyaninato) (octaethylporphyrinato)europium(III)"Chem. Lett.. 944-945 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagao Kobayashi: "Optically active phthalocyanines"Coord. Chem. Rev.. 219-221. 99-123 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] V.N.Nemykin: "Mossbauer, Crystallographic, and Density Functional Theoretical Investigation of the Electronic Structure of Bis-Ligated Low-Spin Iron (II) Phthalocyanones"Eur. J. Inorg. Chem.. 733-743 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagao Kobayashi: "Extremely Non-planar Phthalocyanines with Saddle or Helical Conformation : Synthesis and Structural Characterizations"J. Am. Chem. Soc.. 123. 10740-10741 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuyuki Ishii: "Time-Resolved EPR, Fluorescence, and Transient Absorption Studies on Phthalocyaninatosilicon Covalently Linked to One or Two TEMPO Radicals"J. Am. Chem. Soc.. 123. 702-708 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuyuki Ishii: "Observation of the predicted Negative Faraday A MCD Term in a Cyclobutadiene Dianion"J. Am. Chem. Soc.. 123. 5356-5357 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuyuki Ishii: "Conditions for forming excited multiplet states : magnetic interactions between excited triplet (phthalocyaninato)zinc and doublet nitroxide radical"J. Chem. Soc., Dalton Trans.. 3227-3231 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuyuki Ishii: "Relationship between Electron Spin Polarization, Electron Exchange Interaction, and Lifetime : The Excited Multiplet States of Phthalocyaninatosilioon Covalently Linked to One Nitroxide Radical"J. Phys. Chem.A. 105. 6794-6799 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagao Kobayashi: "Molecular orbitals and electronic spectra of benzo-fused and related porphyrin analogues"J. Porphyrins Phthalocyanines. 5. 233-235 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagao Kobayashi: "The first phthalocyanie-based dimer formed by two pyridine-Pd-pyridine bridges"Tetrahedron Lett.. 42. 913-915 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hideya Miwa: "Spectroscopy, Electrochemistry, and Molecular Orbital Calculations of Metal-Free Tetraazaporphyrin, -chlorin, -bacteriochlorin, and -isobacteriochlorin"Chem. Eur. J.. 1082-1090 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuyuki Ishii: "A Novel Phthalocyanine-based Dimer Linked by a Silver Ion : Structural Control of Self-assembled Dimers"Chem. Lett.. (in press). (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuyuki Ishii: "Exciton interactions in a self-assembled phthalocyanine dimer"J. Chem. Soc., Dalton Trans.. (in press). (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagao Kobayashi: "The Porphyrin Handbook Vol.2"Academic Press, San Diego. 301-360 (2000)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagao Kobayashi: "The Porphyrin Handbook"Academic Press, San Diego (in press).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuyuki Ishii: "The Porphyrin Handbook"Academic Press, San Diego (in press).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Kazuyuki Ishii: "Experimental Evidence for a Selection Rule of Intersystem Crossing to the Excited Quartet States: Metallophthalocyanines Coordinated by 4-Amino-TEMPO"J. Phys. Chem. A.. 103. 6060-6062 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hideya Miwa: "A Novel Phthalocyanine Isomer: A Dinaphthophthalocyanine with C2v Symmetry"Chem. Lett.. 1303-1304 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hideya Miwa: "Synthesis, Spectroscopy, Electrochemistry, and Mesomorphism of Triple-Decker Porphyrins Consisting of Two Cerium Ions and Three 5,15-Diarylporphyrins"Bull. Chem. Soc. Jpn.. 72. 2719-2728 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagao Kobayashi: "Substituent-Induced Circular Dichroism in Phthalocyanines"J. Am. Chem. Soc.. 121. 12018-12028 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagao Kobayashi: "Phthalocyanines"Current Opinion in Solid State and Material Science. 4. 345-353 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagao Kobayashi: "Phthalocyanine Macromolecule - Macromolecule utilized in various fields"Kagaku to Kogyo. 52. 968-971 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagao Kobayashi: "A mutually perpendicular phthalocyanine pentamer obtained by a one-step reaction"Chem. Commun.. 1855-1856 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] V.N. Nemykin: "Low Symmetrical Phthalocyanines Having Spectroscopic and Electrochemical Properties Characteristic of Unexpected Accidental S1 state Degeneracy and Non-Planar Distortion"Chem. Lett.. 184-185 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] V.N. Nemykin: "The Solid Phase, Room-Temperature Synthesis of Metal-free and Metallophthalocyanines, Particularly of 2,3,9,10,16,17,23,24-Octacyanophthalocyanines"Chem. Lett.. 546-547 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] V.N. Nemykin: "Diels-Alder Reaction of Tribenzo [b,g,f] porphyrazine as a New Path for Porphyrazine Core Modification"Chem. Lett.. 1236-1237 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuyuki Ishii: "The excited multiplet states of metalloporphyrins and metallophthalocyanines coordinated or linked to nitroxide radicals"Coord. Chem. Rev.. 198. 231-250 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuyuki Ishii: "Time-Resolved Electron Spin Resonance of Gallium and Germanium Porphyrins in the Excited Triplet State"Inorg. Chem.. 39. 468-472 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagao Kobayashi: "Symmetry-Lowering of the Phthalpcyanine Chromophore by a C2 type Axial Ligand"Inorg. Chem.. 39. 2256-2257 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagao Kobayashi: "Band Deconvolution Analysis of the Absorption and Magnetic Circular Dichroism Spectral Data of a Planar Phthalocyanine Dimer"Inorg. Chem.. 39. 3632-3637 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagao Kobayashi: "Theoretical interpretation of spectroscopic data"J. Porphyrins Phthalocyanines. 4. 377-379 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Taro Nonomura: "Synthesis and some spectroscopic properties of tetra-2,3-pyridinoporphyrazinatosilicon involving bulky axial ligands"J. Porphyrins Phthalocyanines. 4. 538-543 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] V.N. Nemykin: "Synthesis and spectroscopic properties of new phthalocyanine complexes with potentially combined photodynamic activity and cytotoxicity for photodynamic therapy"J. Porphyrins Phthalocyanines. 4. 551-554 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] V.N. Nemykin: "First direct calculation of the partial quadrupole splitting of ligands for the prediction of Mossbauer spectra parameter in low spin iron(II) complexes"Mendeleev Comm.. 2. 43-82 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuyuki Ishii: "The photoexcited multiplet states of porphyrin complexes linked to nitroxide radicals-Evaluation of the excited multiplet states and a new concept for photocontrol of magnetic properties"Kagaku to Kogyo. 54. 144-147 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagao Kobayashi: "A Seven-Membered Carbon-Ring-Fused Phthalocyanine Analogue in which the π System Change during Dehydrogenation/Hydrogenation Cycles"Angew. Chem. Int. ed.. 40. 1300-1303 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagao Kobayashi: "A Novel Hemiporphyrazine Comprising Three Isoindolediimine and Three Thiadiazole Units"Angew. Chem. Int. ed.. 40. 2710-2712 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] V.N. Nemykin: "A tetraazaporphyrin with an intense, broad near-IR band"Chem. Commun.. 165-166 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuyuki Ishii: "Relationship between the Excited Multiplet EPR and Phosphorescence Lifetime in the Excited Triplet Octaethylporphinatozinc Coordinated by One TEMPO Radical"Chem. Lett.. 482-483 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Fumio Furuya: "Synthesis, Structure, and Crystal Characterization of Sandwich-type (2,3 -Naphthalocyaninato) (octaethylporphyrinato) europium(III)"Chem. Lett.. 944-945 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagao Kobayashi: "Optically active phthalocyanines"Coord. Chem. Rev.. 219-221. 99-123 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] V.N. Nemykin: "Mossbauer, Crystallographic, and Density Functional Theoretical Investigation of the Electronic Structure of Bis-Ligated Low-Spin Iron (II) Phthalocyanones"Eur. J. Inorg. Chem.. 733-743 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagao Kobayashi: "Extremely Non-Planar Phthalocyanines with Saddle or Helical Conformation: Synthesis and Structural Characterizations"J. Am. Chem. Soc.. 123. 10740-10741 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuyuki Ishii: "Time-Resolved EPR, Fluorescence, and Transient Absorption Studies on Phthalocyaninatosilicon Covalently Linked to One or Two TEMPO Radicals"J. Am. Chem. Soc.. 123. 702-708 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuyuki Ishii: "Observation of the Predicted Negative Faraday A MCD Term in a Cyclobutadiene Dianion"J. Am. Chem. Soc.. 123. 5356-5357 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuyuki Ishii: "Conditions for forming excited multiplet states: magnetic interactions between excited triplet (phthalocyaninato)zinc and doublet nitroxide radical"J. Chem. Soc., Dalton Trans.. 3227-3231 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuyuki Ishii: "Relationship between Electron Spin Polarization, Electron Exchange Interaction, and Lifetime: The Excited Multiplet States of Phthalocyaninatosilicon Covalently Linked to One Nitroxide Radical"J. Phys. Chem. A.. 105. 6794-6799 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagao Kobayashi: "Molecular orbitals and electronic spectra of benzo-fused and related porphyrin analogues"J. Porphyrins Phthalocyanines. 5. 2233-235 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagao Kobayashi: "The first phthalocyanie-based dimer formed by two pyridine-Pd-pyridine bridges"Tetrahedron Lett.. 42. 913-915 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hideya Miwa: "Spectroscopy, Electrochemistry, and Molecular Orbital Calculations of Metal-Free Tetraazaporphyrin, -chlorin, -bacteriochlorin, and -isobacteriochlorin"Chem. Eur. J.. 1082-1090 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuyuki Ishii: "A Novel Phthalocyanine-based Dimer Linked by a Silver Ion: Structural Control of Self-assembled Dimers"Chem. Lett.. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuyuki Ishii: "Exciton interactions in a self-assembled phthalocyanine dimer"J. Chem. Soc., Dalton Trans.. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagao Kobayashi: "meso-Azaporphyrins and Their Analogues"The Porphyrin Handbook ed by K.M. Kadish, K.M. Smith and R. Guilard, Academic Press, San Diego (2000), Vol. 2. 301-360 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagao Kobayashi: "Synthesis and Spectroscopic Properties of Phthalocyanine Analogues"The Porphyrin Handbook ed by K.M. Kadish, K.M. Smith and R. Guilard, Academic Press, San Diego (in press).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuyuki Ishii: "The Photophysical Properties of Phthalocyanines and Related Compounds"The Porphyrin Handbook ed by K.M. Kadish, K.M. Smith and R. Guilard, Academic Press, San Diego (in press).

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

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Published: 2003-09-17  

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