三重項有機分子の安定化とその複合化による磁性分子素材の構築

• Project/Area Number: 12002007
• Research Category: Grant-in-Aid for Specially Promoted Research
• Allocation Type: Single-year Grants
• Review Section: Chemistry
• Research Institution: Mie University
• Principal Investigator: 富岡 秀雄 三重大学, 工学部, 教授 (20024599)
• Co-Investigator(Kenkyū-buntansha): 高橋 康丈 三重大学, 工学部, 助教授 (70197185) ; 平井 克幸 三重大学, 生命科学研究支援センター, 助教授 (80208793) ; 小関 史朗 大阪府立大学, 総合科学部, 教授 (80252328)
• Project Period (FY): 2000 – 2004
• Project Status: Completed (Fiscal Year 2004)
• Budget Amount: ¥265,300,000 (Direct Cost: ¥217,000,000、Indirect Cost: ¥48,300,000); Fiscal Year 2004: ¥15,600,000 (Direct Cost: ¥12,000,000、Indirect Cost: ¥3,600,000); Fiscal Year 2003: ¥46,800,000 (Direct Cost: ¥36,000,000、Indirect Cost: ¥10,800,000); Fiscal Year 2002: ¥65,000,000 (Direct Cost: ¥50,000,000、Indirect Cost: ¥15,000,000); Fiscal Year 2001: ¥81,900,000 (Direct Cost: ¥63,000,000、Indirect Cost: ¥18,900,000); Fiscal Year 2000: ¥56,000,000 (Direct Cost: ¥56,000,000)
• Keywords: 長寿命三重項カルベン / 速度論的安定化 / ジアゾ化合物 / 光分解 / ESR / SQUID / 高スピンポリカルベン / 有機磁性素材 / ポリジアゾ化合物 / 開殻電子構造 / 熱力学的安定化 / レーザ閃光光分解 / 電子スピン共鳴スペクトル / 磁気的測定

Research Abstract

三重項カルベンは高スピン有機分子の構成単位として有用であることが知られているにも関わらず、不安定であるため、これまで余り利用されてこなかった。我々は三重項カルベンをスピン源として利用する場合のこのような問題を解決するために、(1)三重項カルベンの安定化を行い、完全に安定なものを合成し、(2)それを構成単位として持つ安定な磁性有機分子を構築することを目的としてこの研究を開始した。
(1)三重項カルベンの安定化に関しては、ジアントリルカルベンの10位に嵩高い置換基を導入することによって、室温溶液中でも一週間以上も存在するほぼ完全に安定なものの合成に成功した。又、ジアゾ基を導入した後に更に保護基を被せると言う新しい手法によって幾つかの新しい構造の三重項カルベンの発生にも成功し、幾つかの知見を得た。更に、課題(2)との関連から、ジピリジルカルベンの立体保護による安定化も検討し、かなりの長寿命化に成功した。
(2)有機磁性体の発生源となるポリジアゾ化合物の合成を、園頭カップリング反応、鈴木カップリング反応及びアセチレンの金属触媒重合を用いて行い、その光分解によって発生したポリカルベンをSQUID測定により磁気的解析を行った。現在の所、最大スピン多重度は10程度と未だ低いが、連結π系とスピン中心間の距離を改良することにより、より高いスピン多重度が得られるものと考えられる。又、安定三重項カルベンに金属配位子としてピリジル基を導入し、これを銅イオンと錯化させることによって、安定なヘテロスピン系を構築することにも成功した。更に、機能性を持つ磁性有機素材として、フォトクロミズムを示すジアリールエテンへのカルベン前駆体の導入や、複数のジラジカル中心を持つπ系の基底多重度と構造の関連の解明も成果をあげることが出来た。
以上、当初の目標であった安定な三重項有機分子の構築はほぼ実現できたものと考えている。磁性有機分子の構築に関しては、前駆体合成の手法を確立出来たので、近い将来実現できる見通しは示すことが出来たと考えている。

Research Products

• [Journal Article] Preparation of Bis(diazo) Compounds Incorporated into Butadiyne and Thiophene Units and Generation and Characterization of Their Photoproducts (2005)
  • Author(s): Fumika Morisaki
  • Journal Title: Org.Biomol.Chem. 3 Pages: 431-440
• [Journal Article] Preparation of Poly(phenyl)acetylenes Having Diazo Groups and Magnetic Characterization of Poly(carbene) (2005)
  • Author(s): Tetsuji Itoh
  • Journal Title: J.Am.Chem.Soc. 127 Pages: 1650-1651
• [Journal Article] Preparation of Sterically Congested Di(4-pyridyl)diazomethanes and Characterization of Triplet Carbenes from Them (2005)
  • Author(s): Tetsuji Itoh
  • Journal Title: Org.Lett. 7 Pages: 811-814
• [Journal Article] Preparation of Copper Ion Complexes of Sterically Congested Diaryldiazomethanes Having a Pyridine Ligand and Characterization of Their Photoproducts (2005)
  • Author(s): Tetsuji Itoh
  • Journal Title: J.Am.Chem.Soc. 127(in press)
• [Journal Article] Preparation of Bis(diazo) Compounds Incorporated into Butadiyne and Thiophene Units and Generation and Characterization of Bis(carbene) Therefrom (2004)
  • Author(s): Tetsuji Itoh
  • Journal Title: J.Org.Chem. 69 Pages: 5870-5880
• [Journal Article] Di(9-anthryl)carbene Revisited. Product Analysis and Spectroscopic Studies (2004)
  • Author(s): Ken-ichi Yoshida
  • Journal Title: Bull.Chem.Soc.Jpn. 77 Pages: 1509-1522
• [Journal Article] An ESR Insight into the Thermally Activated Structural Relaxation of the Bis(2,4,6-trichloro-phenyl)carbene in Reaction with the Molecular Motion of the Immediate Surroundings (2004)
  • Author(s): Boris P.Makarov
  • Journal Title: Org.Biomol.Chem. 2 Pages: 1834-1837
• [Journal Article] X-Ray Crystal Structure Study of Sterically Congested Diphenyldiazomethanes (2004)
  • Author(s): Takashi Iikubo
  • Journal Title: Eur.J.Org.Chem. Pages: 3004-3010
• [Journal Article] Triplet Diphenylcarbenes Protected by (Trimethylsilyl)ethynyl Groups (2004)
  • Author(s): Tetsuji Itoh
  • Journal Title: J.Org.Chem. 69 Pages: 4238-4244
• [Journal Article] Synthesis of Phenylacetylene Dendrimers Having Sterically Congested Diazo Units As Presursors for Persistent High-Spin Polycarbenes (2004)
  • Author(s): Tetsuji Itoh
  • Journal Title: Eur.J.Org.Chem. Pages: 2991-3003
• [Journal Article] Reaction of Tetramethylpiperidine N-Oxides with Persistent Triplet Diphenylarbenes (2004)
  • Author(s): Jun-ichi Nakajima
  • Journal Title: Org.Biomol.Chem. 2 Pages: 1500-1503
• [Journal Article] Photolysis of 3-(2-Formylphenyl)-3-chlorodiazirine in an Ar Matrix at Low Temperature (2004)
  • Author(s): Norio Nakane
  • Journal Title: J.Org.Chem. 69 Pages: 3538-3545
• [Journal Article] Stannaacetylene (RSn≡SnR) Showing Carbene-like Reaction Modes (2004)
  • Author(s): Wataru Setaka
  • Journal Title: J.Am.Chem.Soc. 126 Pages: 2696-2697
• [Journal Article] Preparation of Oligodiazo Compounds by Using Suzuki Coupling Reaction and Characterization of Their Photoproducts (2004)
  • Author(s): Tetsuji Itoh
  • Journal Title: J.Am.Chem.Soc. 126 Pages: 1130-1140
• [Journal Article] Laser Flash Photolysis Study of Dialkylphenacylsulfonium Salts (2004)
  • Author(s): Koichi Kawamura
  • Journal Title: Chem.Lett. Pages: 148-149
• [Journal Article] Quintet Bis(carbene) from Triplet Diarylcarbenes Introduced on 1,8 Position of Anthracene (2004)
  • Author(s): Yusuke Ohtsuka
  • Journal Title: Org.Lett. 6 Pages: 847-850
• [Journal Article] Triplet Diphenylcarbenes Protected by o-Aryl Groups (2004)
  • Author(s): Kyoko Monguchi
  • Journal Title: J.Am.Chem.Soc. 126 Pages: 11900-11913
• [Book] 有機磁性体の発生材料としてのポリジアゾ化合物の合成。ジアゾ化合物をビルディングブロックとする方法の展開(有機合成科学協会有機合成化学協会誌、63) (2005)
  • Author(s): 伊藤 哲二
  • Publisher: (in press)
• [Book] Tunneling Insertion Reaction of Carbenes(Series on Atomic, Optical, and Plasma Physics, Volume 36) (2004)
  • Author(s): Hideo Tomioka
  • Publisher: Springer
• [Book] Triplet Carbenes (2004)
  • Author(s): Hideo Tomioka
  • Publisher: Wiley, New York
• [Publications] Koichi Kawamura: "Photoinduced Intramolecular Electron Transfer between Carbazole and Bis(Trichloromethyl)-s-Triazine Generating Radicals"J.Phys.Chem.B. 107. 4579-4586 (2003)
• [Publications] Sergei V.Chapyshev: "Photochemical Transformations of Quintet m-Phenylenedinitrenes"Bull.Chem.Soc.Jpn.. 76. 2075-2089 (2003)
• [Publications] Hideo Tomioka: "Photolysis of Regioisomeric Diazides of 1,2-Diphenylacetylenes Studied by Matrix-Isolation Spectroscopy and DFT Calculations"Org.Bioorg.Mol.. 4441-4450 (2003)
• [Publications] Eri Iwamoto: "Triplet Carbene Surviving a Week in Solution at Room Temperature"J.Am.Chem.Soc.. 125. 14664-14665 (2003)
• [Publications] Yusuke Ohtsuka: "Quintet Bis(carbene) from Triplet Diarylcarbenes Introduced on 1,8Position of Anthracene"Org.Lett.. 6. 847-850 (2004)
• [Publications] Tetsuji Itoh: "Preparation of Oligodiazo Compounds by Using Suzuki Coupling Reaction and Characterization of Their Photoproducts"J.Am.Chem.Soc.. 126. 1130-1140 (2004)
• [Publications] Koichi Kawamura: "Laser Flash Photolysis Study of Dialkylphenacylsulfonium Salts"Chem.Lett.. 33. 148-149 (2004)
• [Publications] Wataru Setaka: "Stannaacetylene (RSn=SnR) Showing Carbene-like Reaction Modes"J.Am.Chem.Soc.. 126(印刷中). (2004)
• [Publications] Hideo Tomioka: "Triplet Carbenes : From Fleeting Existence to Attractive Molecular Units"Pure Applied Chem.. 75. 1041-1047 (2003)
• [Publications] Athanassios Nicolaides: "m-Phenylene-linked Bis(biradicals). Generation, Characterization and Computational Studies"J.Photoscience. 10. 165-173 (2003)
• [Publications] 富岡秀雄: "先端化学シリーズ 有機光化学反応における活性種の役割と利用(日本化学会編)"丸善株式会社. 118-127 (2003)
• [Publications] Athanassios Nicolaides: "Photochemistry of Organic Molecules in Isotropic and Anisotropic Media"Marcell Dekker, New York. 133-184 (2003)
• [Publications] Hideo Tomioka: "Reactive Intermediate Chemistry"Wiley, New York. 375-461 (2004)
• [Publications] Hideo Tomioka: "Atom Tunneling Phenomena in Physics, Chemistry and Biology"Springer, Berlin. 147-172 (2004)
• [Publications] Hideo TOMIOKA: "Generation, Reactions and Kinetics of Sterically Congested Triplet Diphenylcarbenes. Effects of Bromine Groups"J. Am. Chem. Soc.. 124. 474-482 (2002)
• [Publications] Tomoki KOSHIYAMA: "Generation, Reaction and Kinetics of Di(naphthyl) carbenes. Effects of Mehtyl Group"J. Phys. Chem. A.. 106. 8797-8806 (2002)
• [Publications] Tomonori ENYO: "Halogen Derivatives of m-Phenylenecarbenonitrene : A Switch in Ground-State Multiplicity"J. Org. Chem.. 67. 5578-5587 (2002)
• [Publications] Takashi IIKUBO: "Generation, Direct Observation and Kinetics of Triplet 9-(1,1,4,4,5,5,8,8-Octamethyl-1,2,3,4,5,6,7,8-octahydroanthryl)phenylcarbene"Org. Lett.. 4. 2261-2264 (2002)
• [Publications] Eiji IIBA: "Di(triptycyl)carbene. A Fairly Persistent Triplet Dialkylcarbene"J. Am. Chem. Soc.. 124. 14308-14309 (2002)
• [Publications] Katsuyuki HIRAI: "Effects of para-Phenyl Group on the Reactivities of Sterically Congested Triplet Diphenylcarbene"Chem. Lett.. 1226-1227 (2002)
• [Publications] Hideo TOMIOKA: "Approach to A Persistent Triplet Carbene"G.Betrand. 103-152 (2002)
• [Publications] Athanassios NICOLAIDES: "The Characterization and Reactivity of Photochemically Generated Phenylee Bis(diradical) Species Revealed by Matrix Spectroscopy and Computational Chemistry"V.Ramamurthy, and K.S.Schanze. 133-184 (2003)
• [Publications] Hideo TOMIOKA: "Triplet Carbenes"R.A.Moss, M.S.Platz, M-Jones, Jr.. (2003)
• [Publications] Hideo TOMIOKA: "Benzylbenzoin Benzyl Ethers as New Photoinitiators"Res. Chem. Intermed. 27. 47-59 (2001)
• [Publications] Yingmo HU: "Spectroscopic and Product Studies of the Effect of para Substituents on the Reactivity of Di(2,6-dimethylphenyl)carbenes"Bull. Chem. Soc. Jpn.. 74. 2207-2218 (2001)
• [Publications] Athanassios NICOLAIDES: "The Elusive Benzocyclobutenylidene : A Combined Comtputation and Experimental Attempt"J. Am. Chem. Soc.. 123. 2870-2876 (2001)
• [Publications] Athanassios NICOLAIDES: "p-Phenylenecarbenonitrene and its Halogen Derivatives. How Does Resonance Interaction Between a Nitrene and a Carbene Center Affect the Overall Electronic Configuration Y"J. Am. Chem. Soc.. 123. 2628-2636 (2001)
• [Publications] Paul R.SERWINSKI: "Connectivity Effects in Isomeric Naphthalenedinitrenes"Org. Lett.. 3. 357-360 (2001)
• [Publications] Masaki KAWANO: "Structure Analysis of a Transient Triplet Carbene Trapped in a Crystal"J. Am. Chem. Soc.. 123. 6904-6908 (2001)
• [Publications] Hideo TOMIOKA: "Generation and Characterization or a Fairly Stable Triplet Carbene"Nature. 412. 626-628 (2001)
• [Publications] Yasutake TAKAHASHI: "Geometrically Strained Carbenes : Interdependence Among Geometry, Spin Multiplicity and Reactivity"J. Synth. Org. Jpn.. 59. 1070-1077 (2001)
• [Publications] Hideo TOMIOKA: "Generation, Reactions and Kinetics of Sterically Congested Triplet Diphenylcarbenes. Effects of Bromine Groups"J. Am. Chem. Soc.. 124. 474-482 (2002)
• [Publications] Tomonori ENYO: "Halogen Derivatives of m-Phenylenecarbenonitrene : A Switch in Ground-State Multiplicity"J. Am. Chem. Soc.. (in press). (2002)
• [Publications] Hiroaki UMEDA: "Parallelization of Routines for Multi-Reference Perturbation Calculation in GAMESS"High Performance Computing Symposium. 4. 27-33 (2002)
• [Publications] Hiroaki UMEDA: "Benchmark Tests on Parallelized MCQDPT2 Caluculations with GAMESS"Information Processing Society of Japan. 42(in press). (2002)
• [Publications] Shiro KOSEKI: "Dissociation Potential Curves bf Low-Lying States in Transition Metal Hydrides. I.Hydrides of Group 4"J. Phys. Chem. A. 106. 785-794 (2002)
• [Publications] Shiro KOSEKI: "Spin-Orbit Splittings in the Third-ROW Transition Elements : Comparison of Effective-Nulcear-Charge and Full Breit-Pauli Calculations"J. Phys. Chem. A. 105. 8262-8268 (2001)
• [Publications] Hiroaki UMEDA: "Benchmark Tests on Parallelized MRMP2 Calculations with GAMESS"Joint Symposium on Parallel Processing. 6. 129-130 (2001)
• [Publications] Hiroaki UMEDA: "Parallelization of Multi-Referense Perturbation Calculations with GAMESS"J. Comput. Chem.. 22・12. 1243-1251 (2001)
• [Publications] Hirohiko KONO: "A Theoretical Study of Electronic Dynamics and Deformation of CO2 in Intense Laser Fields"J. Phys. Chem. A. 105. 5627-5636 (2001)
• [Publications] Azumao TOYOTA: "Ab Initio MCSCF Study on Eight pi-Electron Heterocyclic Conjugated Systems : Energy Component Analysis of the Pseudo-Jahn-Teller Distortion from Planarity"J. Phys. Chem. A. 105. 1334-1342 (2001)
• [Publications] Hideo TOMIOKA: "Carbene Chemistry"G.Bertrand(in press). (2002)
• [Publications] Hirohiko KONO: "Laser Control and Manipulation of Molecules"Edited by Yuichi Fujimura, American Chem. Soc.(in press).
• [Publications] Hideo TOMIOKA: "Strain and Structure of Sterically Congested Triplet Carbenes"Advances in Strained and Interesting Organic Molecules, Vol.8, ED.by B.Halton, JAI Press, Greenwich. 83-112 (2000)
• [Publications] Yingmo Hu: "Effect of para Substituents on the Reactivities of Sterically Congested Triplet Diphenylcarbenes"Chem.Lett.. 94-95 (2000)
• [Publications] Katsuyuki HIRAI: "Generation, Direct Observation and Kinetics of Triplet (2,4,6-Triisopropylphenyl) Phenylcarbene"Chem.Lett.. 398-399 (2000)
• [Publications] Yasutake TAKAHASHI: "Triplet Di (9-anthryl) carbene Undergoes Trimerization"Angew.Chem.Int.Ed.Engl.. 39. 3478-3480 (2000)
• [Publications] Hidetaka ITAKURA: "Generation, Characterization and Kinetics of Triplet Di [1,2,3,4,5,6,7,8-octahydro-1,4:5,8,-di (ethano) anthryl] carbene"J.Org.Chem.. 65. 8797-8806 (2000)
• [Publications] Hidetaka ITAKURA: "Generation and Characterization of Triplet Anthryl (aryl) carbene."Org.Lett.. 2. 2995-2997 (2000)
• [Publications] Shigeru MURATA : "Remarkable Wavelength-Dependent Photoreactions of the Bis (diazo) Ketone Having Inequivalent Diazo Groups : Studies in Fluid Solutions and in Low Temperature Matrixes"J.Org.Chem.. 65. 6082-6092 (2000)
• [Publications] Valerie LEMEE : "Structure/Properties Relationships in Photoinitiators of Polymerization X1. Behavior of New Benzylbenzoin Benzyl Ethers"Eur.Polymer J.. 36. 1221-1230 (2000)
• [Publications] Hideo TOMIOKA: "Stable High-Spin Molecules"Molecular Magnetism.New Magnetic Materials, Ed.by Koichi Itoh and Minoru Kinoshita, Kodansha-Gordon and Breach Science Publishers, Tokyo-Amsterdam. 251-263 (2000)
• [Publications] Keiji HIDA : "Synthesis of Benzotriazole UV Absorbers with Blocked Hydroxy Group and Their Application to UV Curable Paint"Nippon Kagaku Kaishi. 717-723 (2000)
• [Publications] Athanassios NICOLAIDES: "p-Phenylenecarbenonitrene and its Halogen Derivatives. How Does Resonance Interaction Between a Nitrene and a Carbene Center Affect the Overall Electronic Configuration?"J.Am.Chem.Soc.. (in press). (2001)
• [Publications] Paul R.SERWINSKI: "Connectivity Effects in Isomeric Naphthalenedinitrenes"Org.Lett.. (in press). (2001)
• [Publications] Athanassios NICOLAIDES: "The Elusive Benzocyclobutenylidene : A Combined Computational and Experimental Attempt"J.Am.Chem.Soc.. (in press). (2001)
• [Publications] Hideo TOMIOKA : "Benzylbenzoin Benzyl Ethers as New Photoinitiators "Res.Chem.Intermed.. (in press). (2001)