1997 Fiscal Year Annual Research Report

有機スズ化合物の“複合化"による新規TTF縮環系有機合成金属の開発

Research Project

Project/Area Number	08640694
Research Institution	Himeji Institute of Technology
Principal Investigator	山田順一姫路工業大学, 理学部, 助手 (90191311)
Keywords	有機スズ化合物 / 複合化 / 新規TTF縮環系ドナー / 新規有機合成金属 / トリメチルアルミニウム / κタイプ / ヘテロ環 / 三フッ化ホウ素
Research Abstract	新規TTF縮環系有機合成金属を開発するために次の研究を行った。 1.有機スズ化合物とMe_3Alの“複合化"による新規TTF縮環系ドナーの効率的合成法の確立スズでマスクされたジチオラートとエステルをMe_3Al存在下反応させる過程を経て、短段階で既知および新規TTF縮環系ドナーを合成できる方法を開発した。この合成法により、新規TTF縮環系ドナーとしてTTF-DHTTF縮環系ドナー、TTF-DTDT縮環系ドナー、TTF-DSDTF縮環系ドナーの合成に成功した。 2.TTF-DHTTF縮環系ドナーを用いた新規有機合成金属の開発 4種類のTTF-DHTTF縮環系ドナーから10種類の新規有機合成金属を見い出した。さらに、これらの新規有機成金属の内、(EDDH-TTP)_2AuI_2塩の構造解析に成功し、2:1の組成を持つκタイプの金属的錯体であることを明らかにした。この構造を有する金属的な塩は、TTF縮環系ドナーを用いた錯体では初めての例である。 3.TTF-DTDT縮環系ドナーを用いた新規有機合成金属の開発 4種類のTTF-DTDT縮環系ドナーから7種類の新規有機合成金属の開発に成功した。ジアチン環は構造的自由度を有する置換基であるが、TTF誘導体を縮環させることにより金属的錯体が得られることを明らかにした。 4.TTF-DSDTF縮環系ドナーを用いた新規有機合成金属の開発 5種類のTTF-DSDTF縮環系ドナーから4種類の新規有機合成金属の開発に成功した。現在のところ、この系から良質な単結晶は得られていないが、ペレット状態で活性化エネルギーの小さい値を示す錯体が多数得られている。また、TTF骨格の周辺部がヘテロ環の導入によって拡張された新規ドナーの合成が、有機スズ化合物とBF_3の“複合化"による反応を利用することによって達成できることを見い出した。これらのドナーは従来のTTFドナーに比べて、かさ高い構造であるにもかかわらず、ジオキサン環、ジチアン環、ジオキソラン環を有するTTF誘導体から金属的ラジカルカチオン塩および錯体が得られることを明らかにした。

Research Products
(22 results)

All Other

All Publications (22 results)

[Publications] G.Yu.Logvenov: "Anomalous Nernst effect in the mixed state of the two-band organic superconductors κ-(BEDT-TTF)_2Cu[N(CN)_2]Br and κ-(BEDT-TTF)_2Cu(NCS)_2" Physica C. 264. 261-267 (1996)
[Publications] S.Uji: "Rapid oscillation in the organic conductor (TMTSF)_2ClO_4" Phys.Rev.B. 53. 14399-14405 (1996)
[Publications] J.S.Brooks: "Magnet-oscillation in the high-magnetic-field state of (TMTSF)_2ClO_4" Phys.Rev.B. 53. 14406-14410 (1996)
[Publications] J.Yamada: "Synthesis of Unsymmetrical Tetrathiafulvalene Derivatives via Me_3Al-Promoted Reactions of Organotin Compounds with Esters" J.Org.Chem.61. 3987-3995 (1996)
[Publications] G.Yu.Logvenov: "Anomalous Behavior of the Thermoelectric Power in the Vicinity of the Superconducting Transition in the Organic Superconductors κ-(BEDT-TTF)_2Cu(NCS)_2 and κ-(BEDT-TTF)_2Cu[N(CN)_2]Br" J.Phys.I France. 6. 2051-2060 (1996)
[Publications] J.Yamada: "New organic metals based on vinylenedithio-annulated diselenadithiafulvalene derivatives" J.Chem.Soc., Chem.Commun.1955-1956 (1996)
[Publications] J.Yamada: "Radical-cation salts based on TTF(s)-DHTTF (dihydrotetrathiafulvalene) fused donors : electrical conductivities and crystal structure" J.Chem.Soc., Chem.Commun.2517-2518 (1996)
[Publications] J.Yamada: "A Rearrangement Approach to the Synthesis of New Electron Donors : TTF and DSDTF Derivatives with a 1,3-Dioxolane Ring" Tetrahedron Lett.38. 3439-3442 (1997)
[Publications] S.Uji: "Rapid oscillation and Fermi-surface reconstruction due to spin-density-wave formation in the organic conductor (TMTSF)_2PF_6" Phys.Rev.B. 55. 12446-12453 (1997)
[Publications] S.Uji: "Two distinct magnetic oscillation in a high-field spin-density-wave phase for the organic conductor (TMTSF)_2ClO_4" Phys.Rev.B. 55. 14387-14391 (1997)
[Publications] J.Yamada: "PREPARATION AND ELECTRICAL PROPERTIES OF RADICAL CATION SALTS BASED ON 1,3-DITHIANE DERIVATIVES" Mol.Cryst.Liq.Cryst.(Special Issue). 296. 53-59 (1997)
[Publications] K.Ichimura: "STM Spectroscopy of (BEDT-TTF)_2Cu(NSC)_2" Synth.Met.85. 1543-1544 (1997)
[Publications] J.Yamada: "Synthesis of new TTF(s)-fused donors and electrical conductivities of their radical cation salts" Synth.Met.86. 1823-1824 (1997)
[Publications] S.Uji: "Temperature and Magnetic Field Dependences of Rapid Oscillations in Field Induced Spin-Density-Wave Phase for (TMTSF)_2ClO_4" Synth.Met.86. 1909-1910 (1997)
[Publications] K.Nomura: "NMR Study on the Spin-Density Wave Phase for (TMTSF)_2X" Synth.Met.86. 1951-1952 (1997)
[Publications] A.Hoshikawa: "Sliding of the spin-density wave in (TMTSF)_2ClO_4" Synth.Met.86. 2099-2100 (1997)
[Publications] S.Valfells: "^<77>Se NMR Study of the Spin Density Wave State in (TMTSF)_2PF_6" Synth.Met.86. 2109-2110 (1997)
[Publications] N.Matsunaga: "Anisotropic magnetoresistance of (TMTSF)_2Cl_4 in the metallic and SDW state" Synth.Met.86. 2119-2120 (1997)
[Publications] J.Yamada: "New organic metals based on a BEDT-TTF derivative with steric hindrance" J.Mater.Chem.7. 1311-1312 (1997)
[Publications] S.Uji: "ORIGIN OF RAPID OSCILLATION IN THE METALLIC PHASE FOR THE ORGANIC CONDUCTOR (TMTSF)_2ClO_4" Solide State Commun.103. 387-392 (1997)
[Publications] K.Ichimura: "STM Spectroscopy of (BEDT-TTF)_2Cu(NSC)_2" physica C. 282-287. 1895-1896 (1997)
[Publications] S.Nakatsuji: "PREPARATION AND PROPERTIES OF NEW MULTI-SPIN COMPLEXES" Mol.Cryst.Liq.Cryst.306. 409-414 (1997)

1997 Fiscal Year Annual Research Report

有機スズ化合物の“複合化"による新規TTF縮環系有機合成金属の開発

Principal Investigator

山田 順一 姫路工業大学, 理学部, 助手 (90191311)

Research Products

[Publications] G.Yu.Logvenov: "Anomalous Nernst effect in the mixed state of the two-band organic superconductors κ-(BEDT-TTF)_2Cu[N(CN)_2]Br and κ-(BEDT-TTF)_2Cu(NCS)_2" Physica C. 264. 261-267 (1996)

[Publications] S.Uji: "Rapid oscillation in the organic conductor (TMTSF)_2ClO_4" Phys.Rev.B. 53. 14399-14405 (1996)

[Publications] J.S.Brooks: "Magnet-oscillation in the high-magnetic-field state of (TMTSF)_2ClO_4" Phys.Rev.B. 53. 14406-14410 (1996)

[Publications] J.Yamada: "Synthesis of Unsymmetrical Tetrathiafulvalene Derivatives via Me_3Al-Promoted Reactions of Organotin Compounds with Esters" J.Org.Chem.61. 3987-3995 (1996)

[Publications] G.Yu.Logvenov: "Anomalous Behavior of the Thermoelectric Power in the Vicinity of the Superconducting Transition in the Organic Superconductors κ-(BEDT-TTF)_2Cu(NCS)_2 and κ-(BEDT-TTF)_2Cu[N(CN)_2]Br" J.Phys.I France. 6. 2051-2060 (1996)

[Publications] J.Yamada: "New organic metals based on vinylenedithio-annulated diselenadithiafulvalene derivatives" J.Chem.Soc., Chem.Commun.1955-1956 (1996)

[Publications] J.Yamada: "Radical-cation salts based on TTF(s)-DHTTF (dihydrotetrathiafulvalene) fused donors : electrical conductivities and crystal structure" J.Chem.Soc., Chem.Commun.2517-2518 (1996)

[Publications] J.Yamada: "A Rearrangement Approach to the Synthesis of New Electron Donors : TTF and DSDTF Derivatives with a 1,3-Dioxolane Ring" Tetrahedron Lett.38. 3439-3442 (1997)

[Publications] S.Uji: "Rapid oscillation and Fermi-surface reconstruction due to spin-density-wave formation in the organic conductor (TMTSF)_2PF_6" Phys.Rev.B. 55. 12446-12453 (1997)

[Publications] S.Uji: "Two distinct magnetic oscillation in a high-field spin-density-wave phase for the organic conductor (TMTSF)_2ClO_4" Phys.Rev.B. 55. 14387-14391 (1997)

[Publications] J.Yamada: "PREPARATION AND ELECTRICAL PROPERTIES OF RADICAL CATION SALTS BASED ON 1,3-DITHIANE DERIVATIVES" Mol.Cryst.Liq.Cryst.(Special Issue). 296. 53-59 (1997)

[Publications] K.Ichimura: "STM Spectroscopy of (BEDT-TTF)_2Cu(NSC)_2" Synth.Met.85. 1543-1544 (1997)

[Publications] J.Yamada: "Synthesis of new TTF(s)-fused donors and electrical conductivities of their radical cation salts" Synth.Met.86. 1823-1824 (1997)

[Publications] S.Uji: "Temperature and Magnetic Field Dependences of Rapid Oscillations in Field Induced Spin-Density-Wave Phase for (TMTSF)_2ClO_4" Synth.Met.86. 1909-1910 (1997)

[Publications] K.Nomura: "NMR Study on the Spin-Density Wave Phase for (TMTSF)_2X" Synth.Met.86. 1951-1952 (1997)

[Publications] A.Hoshikawa: "Sliding of the spin-density wave in (TMTSF)_2ClO_4" Synth.Met.86. 2099-2100 (1997)

[Publications] S.Valfells: "^<77>Se NMR Study of the Spin Density Wave State in (TMTSF)_2PF_6" Synth.Met.86. 2109-2110 (1997)

[Publications] N.Matsunaga: "Anisotropic magnetoresistance of (TMTSF)_2Cl_4 in the metallic and SDW state" Synth.Met.86. 2119-2120 (1997)

[Publications] J.Yamada: "New organic metals based on a BEDT-TTF derivative with steric hindrance" J.Mater.Chem.7. 1311-1312 (1997)

[Publications] S.Uji: "ORIGIN OF RAPID OSCILLATION IN THE METALLIC PHASE FOR THE ORGANIC CONDUCTOR (TMTSF)_2ClO_4" Solide State Commun.103. 387-392 (1997)

[Publications] K.Ichimura: "STM Spectroscopy of (BEDT-TTF)_2Cu(NSC)_2" physica C. 282-287. 1895-1896 (1997)

[Publications] S.Nakatsuji: "PREPARATION AND PROPERTIES OF NEW MULTI-SPIN COMPLEXES" Mol.Cryst.Liq.Cryst.306. 409-414 (1997)

山田順一姫路工業大学, 理学部, 助手 (90191311)