1994 Fiscal Year Annual Research Report

フラーレンの化学反応と電子材料への応用

Research Project

Project/Area Number	06224209
Research Institution	The University of Electro-Communications
Principal Investigator	野上隆電気通信大学, 電気通信学部, 教授 (80029280)
Co-Investigator(Kenkyū-buntansha)	石田尚行電気通信大学, 電気通信学部, 助手 (00232306)
Keywords	C_<60> / 酸素付加 / ベンザイン付加 / 結晶構造解析 / ジハロカルベン / マススペクトル / 付加反応 / スピンラベル
Research Abstract	C_<60>の付加反応を調べた。C_<60>とメタクロロ過安息香酸との反応で、C_<60>に酸素原子が付加することを見いだした。酸素2付加体を単離し、その^<13>C-NMRスペクトルから、生成物はCs対称性をもつことを明らかにした。これには3つの候補がある。C_<60>とo-ジメトキシベンザインとの1:1付加体の単結晶を作成し、結晶構造解析を行なった。ベンザインはC_<60>の6員環・6員環縮合部分に付加して、シクロブタン環を形成することを証明した。付加したC_<60>部分のC-C結合距離は1.645Åと異常に長いことがわかった。この研究はC_<60>の2+2環化付加反応生成物の結晶構造解析の最初の成功例である。C_<60>誘導体のスピンラベル分子としての応用、あるいは磁性への展開を念頭に置いて、C_<60>に2、2、6、6-テトラメチルピペリジン-1-オキシルラジカル(TEMPO)が付加した分子を合成した。1:1付加体をマルチ付加体から単離し、各種スペクトルから推定した結果、この分子はC_<60>の5員環・6員環縮合部分に付加し、もとの結合は開いていることがわかった。この分子のCVを測定した結果、還元電位はC_<60>にほぼ近く、C_<60>部分の共役が維持されていることを示した。酸化電位はTEMPOそのものより若干大きく、C_<60>の電子吸引性によると思われる。C_<60>の各種ジハロカルベン1:1付加体を単離し、各種のマススペクトル(FAB、ESI、MALDI、LD)を測定した。フラグメンテーションはLD、FAB、MALDIの順番に大きかったが、ESI法では親イオンピークのみ観測された。LDMSではオリゴマー化がおこり、C_<2n>(2n=122〜132と184〜196)のシグナルが観測された。

Research Products
(17 results)

All Other

All Publications (17 results)

[Publications] 野上隆ほか4人: "Spectral Characterization of Anthrocene,Cyclopentadiene,and Dichlorocarbene-C_<60> Adducts" Fullerene Science and Technology. 2. 155-164 (1994)
[Publications] 野上隆ほか4人: "Synthesis and Characterization of C_<60> Adducts with Benzyne,Dichlorocarbene,Dienes,and Oxygen" Transaction of Material Research Society of Japan. 14B. 1181-1184 (1994)
[Publications] 野上隆ほか8人: "A New Organic Ferromagnet:4-Benzylideneamino-2,2,6,6-tetramethylpiperidin-1-oxyl" Chemistry Letters. 29-32 (1994)
[Publications] 野上隆ほか6人: "Synthesis,Structures,and Electrical Properties of the Charge-Transfer Salts of 4,5-Ethylenedithio-4´,5´-..." Journal of Chemical Society,Faraday Transaction. 90. 763-771 (1994)
[Publications] 野上隆ほか3人: "Pyrimidines as Ferromagnetic Exchange Couplers in Dinuclear Oxovanadium (IV) Complexes" Chemistry Letters. 285-288 (1994)
[Publications] 野上隆ほか2人: "Fullerence Aziridine. Facile Synthesis and Spectral Characterization of Fullerene Urethane,C_<60>NCO_2CH_2CH_3" Chemistry Letters. 561-562 (1994)
[Publications] 野上隆ほか5人: "Molecular Ferromagnet,PM〔VO(hfac)_2〕_2 (PM=Pyrimidine,hfac=1,1,1,5,5,5-hexafluoropenta-2,4-dionate),Ferromagnetic...." Chemistry Letters. 685-686 (1994)
[Publications] 野上隆ほか5人: "Synthesis and Structure of Nitrene-C_<60> Adduct,C_<60>Nphth (phth=Phthalimido)" Tetrahedron Letters. 35. 4371-4374 (1994)
[Publications] 野上隆ほか8人: "An Organic Ferromagnet with a Tc of 0.4K:4-(P-Phenylbenzylidene)-Amino-2,2,6,6-tetramethylpiperidin-1-oxyl" Chemistry Letters. 919-922 (1994)
[Publications] 野上隆ほか9人: "Organic Second Order Nonlinear Optical Materials with Transparency in Blue Wavelength Region:Ethylene Derivatives...." Bulletin of the Chemical Society of Japan. 67. 918-923 (1994)
[Publications] 野上隆ほか5人: "Crystal Structures and Electrical Properties of the Radical Salts of Unsymmetrical Denor EOTT (4,5-ethylenedithio...." Journal of Materials Chemistry. 4. 1559-1569 (1994)
[Publications] 野上隆ほか6人: "Synthesis and Spectral Characterization of Difunctional Fullerenes" Fullerene Science and Technology. (発表予定).
[Publications] 野上隆ほか8人: "Intra- and Inter-Molecular Ferromagnetic Interaction of Transition Metal Complexes Containing Pyrimidine or...." Synthetic Metals. (発表予定).
[Publications] 野上隆ほか9人: "New Organic Ferromagnets:4-Arylmethylene amino-2,2,6,6-tetramethylpiperidim-1-oxyl CAryl=Phenyl,4-Biphenylyl,..." Synthetic Metals. (発表予定).
[Publications] 野上隆ほか5人: "Synthesis and Mass Spectra of C_<60>-Dihalocarbene Adducts" Fullerene Science and Technology. (発表予定).
[Publications] 野上隆ほか5人: "Synthesis and Structures of Novel Fused-Ring Systems Containing Six or Seven Sulfur Atoms:..." Bulletin of the Chemical Society of Japan. (発表予定).
[Publications] 野上隆ほか4人: "First X-Ray Structural Determination of Fullerene [2+2] Cyclcadduct" Chemistry Letters. (発表予定).

1994 Fiscal Year Annual Research Report

フラーレンの化学反応と電子材料への応用

Principal Investigator

野上 隆 電気通信大学, 電気通信学部, 教授 (80029280)

Research Products

[Publications] 野上 隆 ほか4人: "Spectral Characterization of Anthrocene,Cyclopentadiene,and Dichlorocarbene-C_<60> Adducts" Fullerene Science and Technology. 2. 155-164 (1994)

[Publications] 野上 隆 ほか4人: "Synthesis and Characterization of C_<60> Adducts with Benzyne,Dichlorocarbene,Dienes,and Oxygen" Transaction of Material Research Society of Japan. 14B. 1181-1184 (1994)

[Publications] 野上 隆 ほか8人: "A New Organic Ferromagnet:4-Benzylideneamino-2,2,6,6-tetramethylpiperidin-1-oxyl" Chemistry Letters. 29-32 (1994)

[Publications] 野上 隆 ほか6人: "Synthesis,Structures,and Electrical Properties of the Charge-Transfer Salts of 4,5-Ethylenedithio-4´,5´-..." Journal of Chemical Society,Faraday Transaction. 90. 763-771 (1994)

[Publications] 野上 隆 ほか3人: "Pyrimidines as Ferromagnetic Exchange Couplers in Dinuclear Oxovanadium (IV) Complexes" Chemistry Letters. 285-288 (1994)

[Publications] 野上 隆 ほか2人: "Fullerence Aziridine. Facile Synthesis and Spectral Characterization of Fullerene Urethane,C_<60>NCO_2CH_2CH_3" Chemistry Letters. 561-562 (1994)

[Publications] 野上 隆 ほか5人: "Molecular Ferromagnet,PM〔VO(hfac)_2〕_2 (PM=Pyrimidine,hfac=1,1,1,5,5,5-hexafluoropenta-2,4-dionate),Ferromagnetic...." Chemistry Letters. 685-686 (1994)

[Publications] 野上 隆 ほか5人: "Synthesis and Structure of Nitrene-C_<60> Adduct,C_<60>Nphth (phth=Phthalimido)" Tetrahedron Letters. 35. 4371-4374 (1994)

[Publications] 野上 隆 ほか8人: "An Organic Ferromagnet with a Tc of 0.4K:4-(P-Phenylbenzylidene)-Amino-2,2,6,6-tetramethylpiperidin-1-oxyl" Chemistry Letters. 919-922 (1994)

[Publications] 野上 隆 ほか9人: "Organic Second Order Nonlinear Optical Materials with Transparency in Blue Wavelength Region:Ethylene Derivatives...." Bulletin of the Chemical Society of Japan. 67. 918-923 (1994)

[Publications] 野上 隆 ほか5人: "Crystal Structures and Electrical Properties of the Radical Salts of Unsymmetrical Denor EOTT (4,5-ethylenedithio...." Journal of Materials Chemistry. 4. 1559-1569 (1994)

[Publications] 野上 隆 ほか6人: "Synthesis and Spectral Characterization of Difunctional Fullerenes" Fullerene Science and Technology. (発表予定).

[Publications] 野上 隆 ほか8人: "Intra- and Inter-Molecular Ferromagnetic Interaction of Transition Metal Complexes Containing Pyrimidine or...." Synthetic Metals. (発表予定).

[Publications] 野上 隆 ほか9人: "New Organic Ferromagnets:4-Arylmethylene amino-2,2,6,6-tetramethylpiperidim-1-oxyl CAryl=Phenyl,4-Biphenylyl,..." Synthetic Metals. (発表予定).

[Publications] 野上 隆 ほか5人: "Synthesis and Mass Spectra of C_<60>-Dihalocarbene Adducts" Fullerene Science and Technology. (発表予定).

[Publications] 野上 隆 ほか5人: "Synthesis and Structures of Novel Fused-Ring Systems Containing Six or Seven Sulfur Atoms:..." Bulletin of the Chemical Society of Japan. (発表予定).

[Publications] 野上 隆 ほか4人: "First X-Ray Structural Determination of Fullerene [2+2] Cyclcadduct" Chemistry Letters. (発表予定).

野上隆電気通信大学, 電気通信学部, 教授 (80029280)

[Publications] 野上隆ほか4人: "Spectral Characterization of Anthrocene,Cyclopentadiene,and Dichlorocarbene-C_<60> Adducts" Fullerene Science and Technology. 2. 155-164 (1994)

[Publications] 野上隆ほか4人: "Synthesis and Characterization of C_<60> Adducts with Benzyne,Dichlorocarbene,Dienes,and Oxygen" Transaction of Material Research Society of Japan. 14B. 1181-1184 (1994)

[Publications] 野上隆ほか8人: "A New Organic Ferromagnet:4-Benzylideneamino-2,2,6,6-tetramethylpiperidin-1-oxyl" Chemistry Letters. 29-32 (1994)

[Publications] 野上隆ほか6人: "Synthesis,Structures,and Electrical Properties of the Charge-Transfer Salts of 4,5-Ethylenedithio-4´,5´-..." Journal of Chemical Society,Faraday Transaction. 90. 763-771 (1994)

[Publications] 野上隆ほか3人: "Pyrimidines as Ferromagnetic Exchange Couplers in Dinuclear Oxovanadium (IV) Complexes" Chemistry Letters. 285-288 (1994)

[Publications] 野上隆ほか2人: "Fullerence Aziridine. Facile Synthesis and Spectral Characterization of Fullerene Urethane,C_<60>NCO_2CH_2CH_3" Chemistry Letters. 561-562 (1994)

[Publications] 野上隆ほか5人: "Molecular Ferromagnet,PM〔VO(hfac)_2〕_2 (PM=Pyrimidine,hfac=1,1,1,5,5,5-hexafluoropenta-2,4-dionate),Ferromagnetic...." Chemistry Letters. 685-686 (1994)

[Publications] 野上隆ほか5人: "Synthesis and Structure of Nitrene-C_<60> Adduct,C_<60>Nphth (phth=Phthalimido)" Tetrahedron Letters. 35. 4371-4374 (1994)

[Publications] 野上隆ほか8人: "An Organic Ferromagnet with a Tc of 0.4K:4-(P-Phenylbenzylidene)-Amino-2,2,6,6-tetramethylpiperidin-1-oxyl" Chemistry Letters. 919-922 (1994)

[Publications] 野上隆ほか9人: "Organic Second Order Nonlinear Optical Materials with Transparency in Blue Wavelength Region:Ethylene Derivatives...." Bulletin of the Chemical Society of Japan. 67. 918-923 (1994)

[Publications] 野上隆ほか5人: "Crystal Structures and Electrical Properties of the Radical Salts of Unsymmetrical Denor EOTT (4,5-ethylenedithio...." Journal of Materials Chemistry. 4. 1559-1569 (1994)

[Publications] 野上隆ほか6人: "Synthesis and Spectral Characterization of Difunctional Fullerenes" Fullerene Science and Technology. (発表予定).

[Publications] 野上隆ほか8人: "Intra- and Inter-Molecular Ferromagnetic Interaction of Transition Metal Complexes Containing Pyrimidine or...." Synthetic Metals. (発表予定).

[Publications] 野上隆ほか9人: "New Organic Ferromagnets:4-Arylmethylene amino-2,2,6,6-tetramethylpiperidim-1-oxyl CAryl=Phenyl,4-Biphenylyl,..." Synthetic Metals. (発表予定).

[Publications] 野上隆ほか5人: "Synthesis and Mass Spectra of C_<60>-Dihalocarbene Adducts" Fullerene Science and Technology. (発表予定).

[Publications] 野上隆ほか5人: "Synthesis and Structures of Novel Fused-Ring Systems Containing Six or Seven Sulfur Atoms:..." Bulletin of the Chemical Society of Japan. (発表予定).

[Publications] 野上隆ほか4人: "First X-Ray Structural Determination of Fullerene [2+2] Cyclcadduct" Chemistry Letters. (発表予定).