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Fabrication and Functions of Molecular Assemblies based on 2D Surface Coordination Chemistry

基于二维表面配位化学的分子组装体的制备和功能

基本信息

批准号：
12440188
负责人：
HAGA Masa-aki
金额：
$ 9.54万
依托单位：
CHUO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2002
项目状态：
已结题

项目摘要

1) Molecular self-assembly of metal complexes on solid surface: The layer-by-layer growth by the use of coordination bond is one of the promising synthetic strategy for the construction of well-defined nanostructure on the surface. Redox-active rod-shaped metal complexes bridged by bis tridentate ligands are stereochemically defined, and therefore these complexes are one of potential candidates for molecular devices. We have synthesized several new Ru/Os complexes containing tridentate 2,6-bis(benzimidazol-2-yl)pyridine with disulfide (bimpy-S) or phosphonate (bimpy-P) groups as a anchoring group. These [M(bimpy-S)(bimpy-P)] or [M(bimpy-P)2] complexes (M = Ru and Os) were self-assembled on gold or ITO electrode. Layer-by-layer growth was achieved by the successive immersion of the solid substrate to [M(bimpy-P)2] complex in CH3CN and Zr(IV) aqueous solution, and monitored by the UV spectra and electrochemical technique. The absorbance of MLCT band at 500 nm was linearly increased with … More increasing the number of layers, at the 2) 2D coordination chemistry at the air-water interface: In order to control the formation of coordination polymer between the metal ion and ligand such as 4,41-bipyridien, "two-dimensional coordination chemistry" at the air-water interface was developed by using the Langmuir-Blodgett technique. Surface pressure-area (p-A) isotherm of amphiphilic ligand, 3,3'-bis(N,N'-dioctadecylamide)-4,4'-bipyridine ( 1 ) , on pure water subphase shows a liquid expanding phase at a molecular area of 0.45 nm2 and then a liquid condensed phase with a limiting molecular area of 0.40 nm2 molecule-1 close to that expected from a molecular modeling. The change of subphase from pure water to aqueous solution containing metal sulfate (MSO4) leads to a large expansion of molecular area, accompanied by a phase transition. The molecular limiting areas are 0.61 nm2 and 0.45 nm2 for the first and second phases of Ni2+, respectively. The AFM images of 1 transferred from Ni2+-contained subphase reveals the sheet domain morphology with rectangle pinholes oriented to the same direction at the transferred surface pressure of 5 mNm-1. Less

1)金属配合物在固体表面的分子自组装：利用配位键逐层生长是在表面构建良好定义的纳米结构的有前途的合成策略之一。由他的三叉戟配体桥接的氧化还原活性棒状金属配合物具有立体化学定义，因此这些配合物是分子器件的潜在候选者之一。我们合成了几种新的Ru/Os配合物，这些配合物含有三叉戟2,6-二（苯并咪唑-2-基）吡啶，以二硫基（bimpy-S）或膦酸基（bimpy-P）作为锚定基。这些[M(bimpy-S)(bimpy-P)]或[M(bimpy-P)2]配合物（M = Ru和Os）在金或ITO电极上自组装。通过在CH3CN和Zr（IV）水溶液中连续浸泡固体衬底至[M(bimpy-P)2]配合物，实现了一层一层的生长，并通过紫外光谱和电化学技术进行了监测。2)空气-水界面二维配位化学：为了控制金属离子与配体（如4,41-联吡啶）之间的配位聚合物的形成，利用Langmuir-Blodgett技术建立了空气-水界面二维配位化学。两亲性配体3,3′-双（N，N′-二十八烷基酰胺）-4,4′-联吡啶(1)在纯水亚相上的表面压力-面积（p-A）等温线显示出分子面积为0.45 nm2的液体膨胀相，然后是分子面积为0.40 nm2的液体冷凝相，分子-1的极限分子面积接近于分子模型的预期。从纯水到含金属硫酸盐（MSO4）水溶液的亚相变化导致分子面积的大幅膨胀，并伴有相变。Ni2+第一相和第二相的分子极限面积分别为0.61 nm2和0.45 nm2。从含Ni2+亚相转移的1的AFM图像显示，在转移的表面压力为5 nm -1时，具有相同方向的矩形针孔的片状畴形貌。少