2001 年度実績報告書

新規な光応答型磁性を持つ色素の開発

研究課題

研究課題/領域番号	11440192
研究機関	東北大学
研究代表者	小林長夫東北大学, 大学院・理学研究科, 教授 (60124575)
研究分担者	石井和之東北大学, 大学院・理学研究科, 助手 (20282022)
キーワード	光磁性 / 励起多重項状態 / ポルフィリン / フタロシアニン / ニトロキシドラジカル
研究概要	本研究では、幾つかのラジカル結合型フタロシアニン(Pc)を合成し、その光磁気的物性の測定を通して、新規な光応答型磁性を持つ色素の開発を目指す。今年度は、PROXYLラジカルが2つ結合したSiPc(R2a)を新規に合成し、ESR、過渡吸収などの測定を行い、以下のことを明らかにした。 (1)基底状態ESR TEMPOラジカル結合型SiPc(R2c)と異なり、R2aの20KにおけるESRスペクトルは、三重項を示した。そのゼロ磁場分裂(D=40G)から、常磁性中心間の距離は11A^^○と見積もられ、これは最適化構造と一致した。一方、室温においてはスピン相関ラジカル対のESRパターンを示し、基底重項(S_0)-三重項(T_0)間分裂は(8160)1610^<-3>cm^<-1>と見積もられた。 (2)光励起後の磁気的性質の変化R2aの時間分解ESR(TRESR)を測定したところ、速い時間のスペクトルはS_0に、遅い時間のスペクトルはT_0に選択的分布させることで上手く再現された。これは、励起多重項状態からの失活が、速い時間でS_0に、遅い時間でT_0に選択的となることで説明される。S_0への選択的分布は初めての観測例であり、これはSiPcの励起一重項→基底一重項と励起一重項→励起三重項の競争に由来し、比較的強いSiPc-PROXYL間相互作用を反映する。過渡吸収により測定された励起多重項寿命、反転回復法から得られたスピン格子緩和時間を参考にすることで、このTRESR信号の時間変化は良く再現された。

研究成果
(14件)

すべてその他

すべて文献書誌 (14件)

[文献書誌] Nagao Kobayashi: "A seven-Membered Carbon-Ring-Fused Phthalocyanine Analogue in which the π System Changes during Pehydrogenation/Hydrogenation Cycles"Angewante Chemie International Edition. 40. 1300-1303 (2001)
[文献書誌] Nagao Kobayashi: "A Novel Hemiporphyrazine Comprising Three Isoindolediimine and Three Thiadiazole Units"Angewante Chemie International Edition. 40. 2710-2712 (2001)
[文献書誌] V.N.Nemykin: "A tetraazaporphyrin with an intense, broad near-IR band"Chemical Communications. 165-166 (2001)
[文献書誌] Hideya Miwa: "Spectroscopy, Electrochemistry, and Molecular Orbital Calculations of Metal-Free Tetraazaporphyrin, -chlorin, bacteriochlorin, and-isobacteriochlorin"Chemistry A European Journal. (in press).
[文献書誌] Kazuyuki Ishii: "Relatiobship between the Excited Multiplet EPR and Phosphdescence Lifetime in the Excited Triplet Octaethylporphinatozinc Coordinated by One TEMPO Radical"Chemistry Letters. 482-483 (2001)
[文献書誌] Kazuyuki Ishii: "A Novel Phthalocyanine-based Dimer Linked by a Silver Ion : structural Control of Self-Assembled Dimers"Chemistry Letters. (in press).
[文献書誌] Nagao Kobayashi: "Optically active phthalocyanines"Coordination Chemistry Reviews. 219-221. 99-123 (2001)
[文献書誌] Nagao Kobayashi: "Extremely Non-planar Phthalocyanines with saddle or Helical Conformation Synthesis and Structural Characterizations"Journal of the American Chemical Society. 123. 10740-10741 (2001)
[文献書誌] Kazuyuki Ishii: "Observation of the Predicted Negative Faraday A term in a Cyclobutadiene Dianion"Journal of the American Chemical Society. 123. 5356-5357 (2001)
[文献書誌] Kazuyuki Ishii: "Conditions for forming excited multiplet states : magnetic interactions between excited triplet (phthalocyaninato)zinc and doublet nitroxide radical"Journal of Chemical Society, Dalton Transactions. 3227-3231 (2001)
[文献書誌] Kazuyuki Ishii: "Relationship between Election Spin Polarization, Electron Exchange Interaction and Lifetime"The Journal of Physical Chemistry A. 105. 6794-6799 (2001)
[文献書誌] Nagao Kobayashi: "The first phthalocyanine-based dimer formed by two pyridine-Pd-pyridine bridges"Tetrahedron letters. 913-915 (2001)
[文献書誌] Nagao Kobayashi: "The Porphyrin Handbook"Karl M.kadish, Kevin M.Smith, Roger Guilard (in press).
[文献書誌] Kazuyuki Ishii: "The Porphyrin Handbook"Karl M.kadish, Kevin M.Smith, Roger Guilard (in press).

2001 年度 実績報告書

新規な光応答型磁性を持つ色素の開発

研究代表者

小林 長夫 東北大学, 大学院・理学研究科, 教授 (60124575)

研究成果

[文献書誌] Nagao Kobayashi: "A seven-Membered Carbon-Ring-Fused Phthalocyanine Analogue in which the π System Changes during Pehydrogenation/Hydrogenation Cycles"Angewante Chemie International Edition. 40. 1300-1303 (2001)

[文献書誌] Nagao Kobayashi: "A Novel Hemiporphyrazine Comprising Three Isoindolediimine and Three Thiadiazole Units"Angewante Chemie International Edition. 40. 2710-2712 (2001)

[文献書誌] V.N.Nemykin: "A tetraazaporphyrin with an intense, broad near-IR band"Chemical Communications. 165-166 (2001)

[文献書誌] Hideya Miwa: "Spectroscopy, Electrochemistry, and Molecular Orbital Calculations of Metal-Free Tetraazaporphyrin, -chlorin, bacteriochlorin, and-isobacteriochlorin"Chemistry A European Journal. (in press).

[文献書誌] Kazuyuki Ishii: "Relatiobship between the Excited Multiplet EPR and Phosphdescence Lifetime in the Excited Triplet Octaethylporphinatozinc Coordinated by One TEMPO Radical"Chemistry Letters. 482-483 (2001)

[文献書誌] Kazuyuki Ishii: "A Novel Phthalocyanine-based Dimer Linked by a Silver Ion : structural Control of Self-Assembled Dimers"Chemistry Letters. (in press).

[文献書誌] Nagao Kobayashi: "Optically active phthalocyanines"Coordination Chemistry Reviews. 219-221. 99-123 (2001)

[文献書誌] Nagao Kobayashi: "Extremely Non-planar Phthalocyanines with saddle or Helical Conformation Synthesis and Structural Characterizations"Journal of the American Chemical Society. 123. 10740-10741 (2001)

[文献書誌] Kazuyuki Ishii: "Observation of the Predicted Negative Faraday A term in a Cyclobutadiene Dianion"Journal of the American Chemical Society. 123. 5356-5357 (2001)

[文献書誌] Kazuyuki Ishii: "Conditions for forming excited multiplet states : magnetic interactions between excited triplet (phthalocyaninato)zinc and doublet nitroxide radical"Journal of Chemical Society, Dalton Transactions. 3227-3231 (2001)

[文献書誌] Kazuyuki Ishii: "Relationship between Election Spin Polarization, Electron Exchange Interaction and Lifetime"The Journal of Physical Chemistry A. 105. 6794-6799 (2001)

[文献書誌] Nagao Kobayashi: "The first phthalocyanine-based dimer formed by two pyridine-Pd-pyridine bridges"Tetrahedron letters. 913-915 (2001)

[文献書誌] Nagao Kobayashi: "The Porphyrin Handbook"Karl M.kadish, Kevin M.Smith, Roger Guilard (in press).

[文献書誌] Kazuyuki Ishii: "The Porphyrin Handbook"Karl M.kadish, Kevin M.Smith, Roger Guilard (in press).

2001 年度実績報告書

小林長夫東北大学, 大学院・理学研究科, 教授 (60124575)