Electronic functionality of the slipped-stacked assembly structure of the macrocyclic π-ligand complexes

大环π-配体配合物滑移堆叠组装结构的电子功能

• 批准号: 15205018
• 负责人: INABE Tamotsu
• 金额: $ 30.78万
• 依托单位: Hokkaido 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-15205018/
• 关键词: Phthalocyanine; π-stacking structure; partially oxidized salt; electrical conductivity; crystal structure; negative magnetoresistance; 二次元π積層構造

Electrical conductors composed of axially substituted macrocyclic π-ligand metal complexes have following features: I. various π-π stacking networks, II. variation of the electrical properties by the stacking structure, III. π-d interaction and response to the external magnetic field (negative magnetoresistance) on the introduction of magnetic moments. We examined the chemical modification, electron correlation, and dimensionality of the π-n interaction of the phthalocyanine system, and obtained following results.We newly developed a single-step axial ligand exchange method, and a series of the isomorphous one-dimensional conductors were obtained. For the non-magnetic Co system, the axial ligand exchange was found to affect the π-π interaction, while, for the magnetic Fe system, the exchange was found to modify the π-d interaction by shifting the energy of the d-orbitals accommodating the unpaired electron. This is the first example of the tunable π-d system.Though the electronic struc … More ture of the one-dimensional conductors is metallic, the temperature dependence of the charge transport is thermally activated. This was found to be due to the charge-disproportionation from the NQR measurements. The current-voltage characteristics indicated non-linear behavior, suggesting melting of the charge- disproportionation by high electric fields. For the Fe system, more pronounced non-linearity was observed. Therefore, the giant negative magnetoresistance in this system is a reduction of the resistance accompanied by the change from the charge-disproportionation state to spin-aligned state by applying magnetic fields.We also succeeded in obtaining a two-dimensional partially oxidized salt by exchanging the cationic component. The metallic state at low temperature was observed for the Co system under pressure, while abrupt increase of resistivity was observed for the Fe system at 20 K. The π-d interaction in the two-dimensional system is considered to be different from that in the one-dimensional system in which magnetic order is absent. Less

由轴向取代的大环π-配体金属配合物组成的电导体具有以下特点：1 .多种π-π堆叠网络；电性能随堆积结构的变化；引入磁矩时π-d相互作用及对外加磁场（负磁阻）的响应。我们考察了酞菁体系的化学修饰、电子关联和π-n相互作用的维数，得到了以下结果：我们新开发了一种单步轴向配体交换方法，得到了一系列同构的一维导体。对于非磁性Co体系，轴向配体交换影响π-π相互作用，而对于磁性Fe体系，轴向配体交换通过改变容纳未配对电子的d轨道的能量来改变π-d相互作用。这是可调π-d系统的第一个例子。虽然一维导体的电子结构多为金属结构，但电荷输运的温度依赖性是热激活的。这是由NQR测量的电荷歧化引起的。电流-电压特性表现出非线性行为，表明在高电场作用下，电荷歧化现象发生了熔化。对于Fe体系，观察到更明显的非线性。因此，该体系的巨大负磁阻是在外加磁场的作用下，伴随着从电荷歧化状态到自旋排列状态的变化而产生的电阻的减小。我们还成功地通过交换阳离子组分获得了二维部分氧化盐。Co体系在压力下呈现低温金属态，而Fe体系在20k时电阻率急剧升高。二维系统中的π-d相互作用被认为与没有磁序的一维系统中的π-d相互作用不同。少

项目成果

Physical properties of electrically conducting and stable molecular neutral radical solid [Co(2,3-Nc)(CN)2]CH3CN (2,3-Nc = 2,3-naphthalocyanine)

• DOI: 10.1142/s1088424604000611
• 发表时间: 2004-12
• 期刊: Journal of Porphyrins and Phthalocyanines
• 影响因子: 1.5
• 作者: T. Naito;Naoko Matsumura;T. Inabe;Masaki Matsuda;H. Tajima

Structural, Electrical, and Magnetic Properties of π-(ET)_7|MnCl_4|_2AE(1,1,2-C_2H_3Cl_3)_2(ET=Bis(ethylenedithio)tetrathiafulvalene)

π-(ET)_7|MnCl_4|_2AE(1,1,2-C_2H_3Cl_3)_2(ET=双(乙撑二硫)四硫富瓦烯)的结构、电学和磁性

• 发表时间: 2004
• 期刊: Bull.Chem.Soc.Jpn. 77
• 作者: Y.H.Huang;J.Linden;H.Yamauchi;M.Karppinen;T.Naito
• 通讯作者: T.Naito

One-dimensional π-d electoron system in TPP[Fe(Pc)(CN)_2l_2, [PXX][Fe(Pc)(CN)_2l, and (PTMA)_x[Fe(Pc)(CN)_2]Y(CH_3CN) : electron spin resonance and negative magnetoresistance

TPP[Fe(Pc)(CN)_2l_2、[PXX][Fe(Pc)(CN)_2l 和 (PTMA)_x[Fe(Pc)(CN)_2]Y( 中的一维 π-d 电子系统CH_3CN)：电子自旋共振和负磁阻

• 发表时间: 2003
• 期刊: Synth. Met. 133-134
• 作者: M.Karppinen;Y.Morita;J.M.Chen;R.S.Liu;H.Yamauchi;N.Hanasaki
• 通讯作者: N.Hanasaki

Crystal design of cation-radical salts based on the supramolecular self-organizing arrangement of mellitate anions

基于苯三酸根阴离子超分子自组织排列的阳离子自由基盐晶体设计

• 发表时间: 2004
• 期刊: J. Phys. IV France 114
• 作者: S.Takeuchi;O.Nakatsuka;Y.Wakazono;A.Sakai;S.Zaima;Y.Yasuda;Akira Sakakura;Lin Li;T.Inabe
• 通讯作者: T.Inabe

A Voltage Induced Transition of Hemin in BIODE (Biomolecular Light-Emitting Diode)

BIODE（生物分子发光二极管）中血红素的电压诱导转变

• 发表时间: 2006
• 期刊: Bull. Chem. Soc. 79
• 作者: 小夫家芳明;H.Tajima
• 通讯作者: H.Tajima