Surface Nanochemistry for Combinatorial Fabrication of Molecular Multilayered Films Toward Highly Efficient Molecular Devices

对于合成化学家来说，真正的挑战之一是从简单的分子单元开始，通过自组装在固体表面上构建定义良好的纳米级结构或空间。自组装和金属络合自组织的结合有可能在表面提供新的定义良好的纳米结构和功能。在本项目中，我们研究了表面双核金属络合物组件的层层制备及其面向分子器件的电化学功能。合成了一种新型双核Ru/Os配合物[M(XP)(BL)M(XP)](M=Ru和Os)。对双核Ru/Os络合物[M(XP)(BL)M(XP)](M=Ru和Os)在ITO电极上自组装单分子膜的原子力显微镜测量提供了清晰的分子域图像。[M(XP)(BL)M(XP)]络合物在ITO电极上的电化学研究表明，当M=Ru时为0.93V，M=Os时为0.66V，r…时为一步两电子过程更确切地说。通过[M(XP)(BL)M(XP)]中膦酸根与Zr(IV)的配位作用，实现了表面的逐层生长。通过改变具有不同氧化还原电位的模块的顺序，可以构造出朝向分子整流器的不同的电位序列。多层膜上的电子转移行为强烈地依赖于分子内的电势梯度。为了在固体表面构建良好的纳米二维结构，我们研究了DNA模板的Au纳米终端之间的纳米线。配合物中的插层基团为吖啶(ACD)基团。络合物[Ru(XP)(L-ACD)]以分子点的形式固定在云母表面，可以作为DNA的捕获点。我们发现DNA被表面上的分子点捕获了。来自原子力显微镜的测量。此外，在微米级的Au/SiO_2图形硅衬底上的两个Au端子被λ-DNA分子连接，该分子被Pd纳米颗粒金属化。较少

One of the real challenges for synthetic chemists is to construct a well-defined nanometer-sized structure or space on solid surfaces by self-assembly, starting from simple molecular units. The combination of self-assembly with self organization by metal complexation has the potential to provide novel well-defined nanostructures and functions on surfaces. In this project, we have studied the layer-by-layer fabrication and electrochemical function of dinuclear metal complex modules on surface towards molecular devices. New dinuclear Ru/Os complexes, [M(XP)(BL)M(XP)] (M=Ru and Os), with tetrapod free-standing phosphonate ligand (XP) have been synthesized as a building module. The AFM measurement for the self-assembled monolayer of dinuclear Ru/Os complexes, [M(XP)(BL)M(XP)] (M=Ru and Os) on an ITO electrode provides dear molecular domain images. Electrochemistry of [M(XP)(BL)M(XP)] complex on ITO electrode showed a one-step two-electron process at +0.93 V for M=Ru and +0.66 V for M=Os, r … More espectively. Layer-by-layer growth on the surface was achieved by the help of Zr(IV) coordination to the phosphonate groups in [M(XP)(BL)M(XP)]. By changing the order of the modules with different redox potentials, the different potential sequence towards a molecular rectifier can be constructed. The electron transfer behaviors on the multilayer films strongly depend on the potential gradients within the molecular components.In order to construct a well-defined nanometer-sized 2D structure on solid surfaces, we have studied the DNA-templated nanowiring between Au nanoterminals. Acridine (Acd) group was chosen as an intercalating group in the complex. The complex, [Ru(XP)(L-Acd)] was immobilized on mica surface as molecular dots, which can act as a DNA trapping site. We found that DNA was captured by the molecular dots on the surface. From the AFM measurement. Further, two Au terminals on the micrometer-sized Au/SiO_2 patterned silicon substrate were connected by λ-DNA molecules, which was metallized by the Pd nanoparticles.. Less