Solid State Properties of Metal-Assembled Complexes

金属组装配合物的固态特性

• 批准号: 10149103
• 负责人: KATO Reizo
• 金额: $ 53.57万
• 依托单位: RIKEN (1999-2002)The University of Tokyo (1998)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas (A)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10149103/
• 关键词: Photo-induced phase transition; Super conductivity; Magnetic properties; Charge transfer phase transition; Metal complexes; Transport properties; Nonlinear optics; Spin-crossover complexes; 光誘起相転移; 強磁性; 電荷移動相転移; 光物性; 強磁性体; 電荷移動; 光学特性; スピンクロ

We have studied solid state properties of metal-assembled complexes and have obtained the following results;1) Two new Pd(dmit)_2-based molecular superconductors have been found. Electronic states of these systems under pressure have been investigated with X-ray diffraction method and band calculation.2) Two examples of superconductivity induced by uniaxial strain have been found in molecular conductors, (DIETS)_2[Au(CN)_4] and ヲツ'-Me_4As[Pd(dmit)_2]_2, where metal complexes play an important role.3) The first metallic crystals of Ni(tmdt)_2 composed of single component molecules have been synthesized and characterized.4) The first examples of metallic systems interacting with ferromagnetic spins, (EDO-TTF)_2M(mnt)_2 (M=Ni, Pt), have been found. For (DMET)_2FeBr_4, a direct evidence of the ヲミ-d interaction particularly enhanced around the M-I transition has been obtained by the magnetoresistance measurements.5) The newly synthesized mixed-valence complex [(n-Pr)_4N][Fe^<II>Fe^<III>(dto)_3] has been revealed that the system shows the ferromagnetic transition at 6.5 K and the reversible charge transfer phase transition at about 120 K.6) We have prepared several [Fe(4-R=z)_3] complex films by using ion-exchange films such as Nafion film as counter anion, and have revealed that these films show the spin-crossover phenomenon near the room temperature.7) The dynamical study on the photo-effect under magnetic field in organic Fe(II) complex which shows the spin-crossover transition has revealed that the cooperative interaction plays an important role in the dynamic process of the photoconversion.8) Gigantic optical nonlinearity has been found in the one-dimensional (1D) Mott insulators, halogen-bridged Ni complexes, with electro-reflectance measurements, which strongly indicates a high potential for new optoelectronic materials of the 1D Mott-insulators.

我们研究了金属组装配合物的固态性质，得到以下结果：1）发现了两种新的Pd（dmit）_2基分子超导体，用X射线衍射方法和能带计算研究了它们在压力下的电子态。2）发现了两个由单轴应变诱导的分子超导体的例子，（DIETS）_2[Au（CN）_4]和双金属配合物-Me_4As[Pd（dmit）_2]_2，其中金属配合物起着重要的作用; 3）首次合成并表征了Ni（tmdt）_2的单组分金属晶体; 4）首次报道了与铁磁自旋相互作用的金属体系，（EDO-TTF）_2M（mnt）_2（DMET）_2FeBr_4的磁电阻测量结果表明：（DMET）_2FeBr_4的磁电阻效应在M-I转变附近增强; 5）新合成的混合价配合物[（n-Pr）_4N][Fe^<II>Fe^<III>（dto）_3]结果表明，该体系在6.5K左右发生铁磁相变，在120 K左右发生可逆的电荷转移相变。6）用离子注入法制备了几种[Fe（4-R=z）_3]配合物薄膜。交换膜如Nafion膜作为抗衡阴离子，7）对有机Fe（II）配合物在磁场作用下的光效应进行了动力学研究，发现了自旋交叉跃迁，表明协同作用在光转化的动力学过程中起着重要的作用。通过电反射测量，在一维（1D）莫特绝缘体（卤素桥连Ni配合物）中发现了巨大的光学非线性，这强烈表明一维莫特绝缘体新型光电材料的高潜力。

项目成果

M.Enomoto, T.Enoki, et al.: "Magnetic Properties of Mixed Crystal (C_1TET-TTF) (FeBr_4)_<1-x>(FeCl_4)_x"Synth. Metals. 121・1-3. 1800-1801 (2001)

M.Enomoto、T.Enoki 等：“混合晶体 (C_1TET-TTF) (FeBr_4)_<1-x>(FeCl_4)_x”金属 121・1-3。 (2001)

R.Kato: "Conductive Copper salts of 2,5-Disubstituted N, N'-Dicyanobenzoquinonediimines (DCNQIs) : Structural and Physical Properties"Bull. Chem. Soc. Jpn.. 73・3. 515-534 (2000)

R.Kato：“2,5-二取代的 N,N-二氰基苯醌二亚胺 (DCNQI) 的导电铜盐：结构和物理性质”Soc Jpn. 73・3。

Y.Nishio, R.Kato, et al.: "Thermodynamical Study of (DMe-DCNQI)_2Cu System -Mechanism of Reentrant Metal-Insulator Transition--"J. Phys. Soc. Jpn.. 69・5. 1414-1422 (2000)

Y.Nishio、R.Kato 等：“(DMe-DCNQI)_2Cu 体系的热力学研究 - 重入金属-绝缘体转变的机制 -”J. Phys Jpn.. 69・5。 (2000)

R.Kato, et al.: "Conducting Properties of Assembled Metal Complexes"Mol. Cryst. Liq. Cryst.. 343. 1-8 (2000)

R.Kato 等人：“组装金属配合物的导电性能”Mol。

H.Kishida, K.Fujinuma, H.Okamoto: "Electromodulation spectroscopy in ferroelectric CT complex : TTF-CA"Synth. Met.. 120. 909-910 (2001)

H.Kishida、K.Fujinuma、H.Okamoto：“铁电 CT 复合体中的电调制光谱：TTF-CA”Synth。