Development of Self-Assembling Nanowires Consisted of One-Dimensional Metal Complexes

一维金属配合物自组装纳米线的研制

• 批准号: 13440210
• 负责人: KIMIZUKA Nobuo
• 金额: $ 9.22万
• 依托单位: Kyushu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13440210/
• 关键词: self-assembly; one-dimensional complex; band gap engineering; mixed-valence complex; organogel; spintransition; ナノ金属錯体; 電荷移動吸収; サーモクロミズム; ゾルゲル転移; ハニカム構造; 電子構造エンジニアリング; 金属ナノ粒子; 一次元ナノ構造; 自己組織性; 超分子組織体; 脂質被覆型金属ナノ粒子; 白金混合原子価錯体; 一次元ナノワイヤ; バン

The design and synthesis of electronically conjugated molecular wires are one of the important areas in chemistry due to their potential applications in nano-electronic devices. Quasi-one-dimensional, halogen-bridged mixed-valence complexes[Pt(en)_2][PtX_2(en)_2](ClO_4)_4(X=Cl,Br,I) are low-dimensional solids with the metal atoms in alternating valence(charge density wave,CDW) states. The linear complexes have been available only as structural motifs of bulk crystals, and they were not considered as candidates for the molecular wires.In this study, a novel class of chiral supramolecular assemblies is formed from chloro-bridged, mixed valence complex of platinum and newly developed chiral lipids. When ternary complexes of[Pt(en)_2][PtCl_2(en)_2](lipid)_4 are dispersed in dichloromethane, indigo-colored dispersions are obtained. The color is ascribed to the intervalence charge transfer(CT) absorption of the chloro-bridged complexes, indicating the maintenance of one-dimensional coordinat … More ion structures in solution. Circular dichroism(CD) spectra of these dispersions give intense Cotton effects at 490nm and at 600nm with opposite signs. They are assigned to the induced CD(ICD), since they are observed for the CT absorption bands of the achiral complexes and are in mirror symmetry with respect to the chirality of lipids. Nanocrystals with lamellar supramolecular structures are observed in transmission electron microscopy(TEM) and in high resolution TEM(HRTEM). Upon heating the indigo-colored dispersions to 30℃, fading of the indigo color occurred. Interestingly, the indigo-color is restored after cooling and formation of chiral nanocoils with widths of ca. 40nm and pitches of ca. 20nm are observed by atomic forcemicroscopy(AFM). The sense of these nanocoils is dependent on chirality of the amphiphiles, in good agreement with the observed ICD spectra. The supramolecular self-assembly of linear metal complexes and chiral molecular assemblies would be widely applied to the development of chiral organic/inorganic nanoarchitectures. Less

由于其在纳米电子器件中的潜在应用，电子共轭分子线的设计和合成是化学研究的重要领域之一。准一维卤素桥联混合价complexes[Pt(en)_2][PtX_2(en)_2](ClO_4)_4(X=Cl，(BR，I)是金属原子处于交替价态(电荷密度波)的低维固体。在本研究中，一类新型的手性超分子组合物是由氯桥联的铂的混合价配合物与新开发的手性脂类化合物形成的。将[Pt(En)_2][PtCl2(En)_2](Lid)_4的三元络合物分散在二氯甲烷中，得到了深蓝色的分散体。这种颜色归因于氯桥络合物的价间电荷转移(CT)吸收，表明一维坐标…保持不变溶液中有更多的离子结构。这些分散体的圆二向色性(CD)光谱在490 nm和600 nm处表现出强烈的Cotton效应，但符号相反。它们被归类为诱导CD(ICD)，因为它们是在无手性络合物的CT吸收带上观察到的，并且相对于脂类的手性是镜像对称的。在透射电子显微镜和高分辨电子显微镜中观察到具有层状超分子结构的纳米晶体。当将蓝颜色的分散体加热到30℃时，蓝颜色发生褪色。有趣的是，冷却后蓝蓝色被恢复，原子力显微镜(AFM)观察到宽度约为40 nm、间距约为20 nm的手性纳米线圈的形成。这些纳米线圈的感觉取决于两亲分子的手性，这与观察到的ICD光谱很好地一致。线性金属络合物和手性分子组装的超分子自组装将广泛应用于手性有机/无机纳米结构的开发。较少

项目成果

Tetsu YONEZAWA: "Controlled Formation of Smaller Gold Nanoparticles by the Use of Four-ChainedDisulfide Stabilizer"Langmuir. 17・2. 271-273 (2001)

Tetsu YONEZAWA：“使用四链二硫化物稳定剂控制较小的金纳米粒子的形成”Langmuir 17・2（2001）。

T.Yonezawa et al.: "Controlled Formation of Smaller Gold Nanoparticles by the Use of Four-Chained Disulfide Stabilizer"Langmuir. 17・2. 271-273 (2001)

T. Yonezawa 等人：“使用四链二硫化物稳定剂控制较小的金纳米颗粒的形成”Langmuir 17・2 (2001)。

N.Kimizuka et al.: "Spontaneous Self-assembly of Glycolipid Bilayer Membranes in Sugar-philic Ionic Liquids and Formation of Ionogels"Langmuir. 17・22. 6759-6761 (2001)

N. Kimizuka 等人：“亲糖离子液体中糖脂双层膜的自发自组装和离子凝胶的形成”Langmuir 17・22 (2001)。

T.Nakashima et al.: "Light-Harvesting Supramolecular Hydrogels Assembled from Short-Legged Cationic L-Glutamate Derivatives and Anionic Fluorophores"Adv.Mater.. 16・14. 1113-1116 (2002)

T. Nakashima 等人：“由短腿阳离子 L-谷氨酸衍生物和阴离子荧光团组装的光捕获超分子水凝胶”Adv. 16・1116 (2002)

T.Yonezawa, N.Kimizuka et al.: "Formation of an Isolates Spherical Three-Dimensional Nanoparticle Assembly as Stable Submicrometer-Sized Units an Inorganic Wrapping Technique"Adv.Mater.. 15・6. 499-503 (2003)

T. Yonezawa、N. Kimizuka 等：“作为稳定的亚微米尺寸单元的分离球形三维纳米粒子组装体的无机包裹技术” Adv. 15・6 (2003)