Development of Multifunctional Organic Materials (Superconductors, Spin Liquids, Novel Phase Transition Systems, etc)

多功能有机材料（超导体、自旋液体、新型相变系统等）的开发

• 批准号: 15205019
• 负责人: SAITO Gunzi
• 金额: $ 32.78万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15205019/
• 关键词: Organic Superconductor; Uniaxial Strain; Metal-Insulator Transition; Photo-Induced Phase Transition; Ionic Liquid; Nucleobase-Conductor; Amphoteric Compound; Fullerene; スピン液体; イオン性液体

Systematic uniaxial strain study of κ-(BEDT-TTF)_2X revealed the relationship between the anisotropy of the triangular spin lattice and superconducting transition temperature. We discovered the spin liquid behavior in the Mott insulator κ-(BEDT-TTF)_2Cu_2(CN)_3 which has the nearly regular triangular spin lattice.We demonstrated the ultra-fast and highly efficient photo-induced metal-insulator transition system in (EDO-TTF)_2PF_6, where one photon converts ca. 500 molecules to highly conducting state within 1.5 ps. TP-EDOT, a new donor having thiopyrane and dithiol rings, gave a Mott insulator exhibiting a unique magnetic structure.A (C_<60>^-)_2 dimer bound by two C-C bonds was prepared for the first time in an ionic {(MDABCO^+)・Co^<II>TMPP}_<2・ (C_<60>^-)_2・(C_6H_4Cl_2)_<2.5>・(C_6H_5CN)_<1.5>, the magnetic behavior of which was interpreted by the singlet-triplet model. A reversible formation of a coordination Co-C(C_<60>^-) bond was found in {(MDABCO^+)・Co^<II>OEP・(C_<60>^-)}・ (C_6H_ … More 5CN)_χ・(C_6H_4Cl_2)_<1-χ>, The bond formation was accompanied by a paramagnetic-diamagnetic transition.1-Alkyl(C_nH_<2n+1>)-3-methylimidazolium (C_nMI) cations afforded 8 and 4 paramagnetic ionic liquids based on Fe^<III>X_4 (X : Cl, Br) anions and organic anions with TEMPO radical moiety, respectively. Au^I(CN)_2 salts composed of C_nMI cations having elongated alkyl chains (n 【greater than or equal】 4) emitted blue lights in liquid form at room temperature. Also, we obtained a new C_4MI salt formed with pyrene-based anion, which melts at 43 ℃ and exhibits a blue-green emission in the liquid state.We prepared indoline-TCNQ intramolecular charge transfer compounds having various substituents to establish the methodologies to control and estimate their charge transfer degree. Chemical modification on pyrimido-fused TTF derivatives yielded conductive single-component organic compounds. Complex formation between cytosine and TCNQ derivatives afforded charge transfer salts exhibiting self-assembled structures and high conductivity. Less

对κ-(BEDT-TTF)_2X进行了系统的单轴应变研究，揭示了三角自旋晶格各向异性与超导转变温度之间的关系。我们发现了具有近规则三角形自旋晶格的Mott绝缘子κ-(BEDT-TTF)_2Cu_2(CN)_3的自旋液体行为。我们在（EDO-TTF）_2PF_6中展示了超快速高效的光诱导金属-绝缘体转变系统，其中一个光子在1.5 ps内将大约500个分子转化为高导态。TP-EDOT是一个具有硫代嘌呤和二硫醇环的新供体，它使Mott绝缘体具有独特的磁性结构。首次在离子{（MDABCO^+）·Co^<II>TMPP}_<2·（C_<60>^-）_2·（C_6H_4Cl_2）_<2.5>·（C_6H_5CN）_<1.5>中制备了由两个C-C键结合的（C_<60>^-）_2二聚体，并用单重态-三重态模型解释了其磁性行为。在{（MDABCO^+）·Co^<II>OEP·（C_<60>^-）}·（C_6H_…More 5CN）_χ·（C_6H_4Cl_2）_<1-χ>中发现了可逆的配位Co- c （C_<60>^-）键，键的形成伴随着顺磁-反磁转变。1-烷基(C_nH_<2n+1>)-3-甲基咪唑（C_nMI）阳离子分别以Fe^<III>X_4 （X: Cl, Br）阴离子和TEMPO自由基部分的有机阴离子为基础，提供了8和4个顺磁性离子液体。Au^I(CN)_2盐由具有细长烷基链（n【大于或等于】4）的C_nMI阳离子组成，在室温下呈液态发出蓝光。同时，我们得到了一种新的以芘基阴离子形成的C_4MI盐，该盐在43℃熔化，呈蓝绿色发光。制备了具有不同取代基的吲哚- tcnq分子内电荷转移化合物，建立了控制和估计其电荷转移度的方法。对嘧啶-熔融TTF衍生物进行化学改性，得到导电的单组分有机化合物。胞嘧啶和TCNQ衍生物之间形成的络合物提供了具有自组装结构和高导电性的电荷转移盐。少

项目成果

Ionic liquids based on dicyanamide anion: influence of structural variations in cationic structures on ionic conductivity.

• DOI: 10.1021/jp067055t
• 发表时间: 2007-01
• 期刊: The journal of physical chemistry. B
• 作者: Y. Yoshida;Osamu Baba;G. Saito

Hydrogen-bonded networks in organic conductors: crystal structures and electronic properties of charge-transfer salts of tetracyanoquinodimethane with 4,4'-biimidazolium having multiprotonated States.

• DOI: 10.1021/jo047768c
• 发表时间: 2005-04
• 期刊: The Journal of organic chemistry
• 作者: Y. Morita;T. Murata;K. Fukui;S. Yamada;Kazunobu Sato;D. Shiomi;T. Takui;H. Kitagawa;H. Yamochi;G. Saito;K. Nakasuji

Spin liquid state in an organic Mott insulator with a triangular lattice

• DOI: 10.1103/physrevlett.91.107001
• 发表时间: 2003-09-05
• 期刊: PHYSICAL REVIEW LETTERS
• 影响因子: 8.6
• 作者: Shimizu, Y;Miyagawa, K;Saito, G
• 通讯作者: Saito, G

Phase transition from Mott insulating phase into charge ordering phase with molecular deformation in the charge transfer salts κ-(BEDT-TTF)_4[M(CN)_6][N(C_2H_5)_4]・2H_2O(M=Co^<III> and Fe^<III>).

电荷转移盐中分子变形，从莫特绝缘相到电荷有序相的相变 κ-(BEDT-TTF)_4[M(CN)_6][N(C_2H_5)_4]·2H_2O(M=Co^<III>和 Fe^<III>)。

• 发表时间: 2007
• 期刊: Chemistry of Materials 19(10)
• 作者: K.Ariga;et al.;A.Ota
• 通讯作者: A.Ota

Dicyanoaurate(I) salts with 1-alkyl-3-methylimidazolium : Luminescent properties and room-temperature liquid forming.

二氰基金酸盐 (I) 与 1-烷基-3-甲基咪唑鎓盐：发光特性和室温液体形成。

• 发表时间: 2006
• 期刊: Journal of Materials Chemistry 16(8)
• 作者: J.J.Kim;H.Makino;T.Yano;Y.Takata;K.Kobayashi;T.Yamamoto;T.Hanada;et al.;M.Oogane;Y.Yoshida
• 通讯作者: Y.Yoshida