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

1)金属络合物在固体表面的分子自组装：利用配位键逐层生长是在固体表面构建规整纳米结构的一种很有前途的合成策略。由双三齿配体连接的氧化还原活性棒状金属络合物是立体化学定义的，因此这些络合物是潜在的分子器件候选之一。我们合成了几种新的含三齿2，6-二(苯并咪唑-2-基)吡啶和二硫键(bimpy-S)或膦酸基(bimpy-P)的Ru/Os配合物。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。通过将固体衬底连续浸泡到[M(bimpy-P)2]的CH3CN和Zr(IV)水溶液中实现了层层生长，并通过紫外光谱和电化学技术进行了监测。5 0 0 nm处多层螺旋CT谱带的吸光度随…的增加呈线性增加进一步增加层数，在气-水界面的二维配位化学：为了控制金属离子与4，41-联吡二烯等配位聚合物的形成，利用Langmuir-Blodgett技术发展了气-水界面的二维配位化学。两亲配体3，3‘-双(N，N’-二十八胺)-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 nm~2的液体膨胀相，然后是极限分子面积为0.40 nm~2分子~(-1)的液体凝聚相。亚相从纯水转变为含有金属硫酸盐(MSO4)的水溶液，导致分子面积的大幅膨胀，伴随着相变。Ni2+第一相和第二相的分子极限面积分别为0.61nm2和0.45nm2。从含Ni2+的亚相转移到1的AFM图像显示，在转移表面压力为5 MNM-1时，1具有相同方向的矩形针孔的片状微区形态。较少

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