Construction of Electro-functional Space Using Interfacial Bottom-up Synthesis of Coordination Bond Network

在这个项目中，我们的目标是通过组装pi-聚合和/或redox活性金属复合体分子链在一个、两个或三个维度上的结构来构建电功能界面空间。自下而上的方法使用成功的协调结合形成可以按顺序使用，以便在任何潜在的分布中创建空间，可以由外部刺激（如电子和光子）控制。Fe的线性和分支聚体电线的电影（TPY）2（tpy = 2，2' ：6'，2"-terpyridine） were constructed on a gold electrode surface by the interfacial stepwise coordination method employing a surface-anchoring ligand，（tpy-C6H4N= NC6H4-S） 2 （1）、two bridging ligands、1、4-C6H4（tpy）2 （3） and 1、3、5-C6H3（C·C-tpy）3 （4）、and metalions。配体和FeII的定量复合物是通过3个以上到8个复合体的线性分子和4个以上到4个循环的分支分子的电化学测量来监测的。STM观察的分支分子在低表面覆盖显示任何具有均匀大小和形状的纳米点分布，并建议Dendritic结构的定量形成。The electron transport Mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential step chronoamperometry （PSCA）。独特的i-t行为，类似于在所有条件下发现的电子行为指标，而不是通过不同的运动，而是通过成功的电子跳跃在分子线内邻近的redox站点之间。这是redox聚合物films中的第一个观察redox conduction。Other studies such as fabrication of Co-Ru wires and anthraquinone-bridged metal complex molecular were also reported。We also constructed a ferrocenylabozenezene SAM which can undergo reversible isomerization with a single greenlight source and a redox reaction。

In this project, we aim at the construction of electro-functional interfacial space by assembling pi-conjugated and/or redox active metal complex molecular chains in one, two, or three dimensions. Bottom-up approach using successive coordination bond formation is utilized in order to create the space in which potential distribution can be controlled by external stimuli such as electrons and photons.Films of linear and branched oligomer wires of Fe (tpy)2 (tpy = 2,2' :6',2" -terpyridine) were constructed on a gold electrode surface by the interfacial stepwise coordination method employing a surface-anchoring ligand, (tpy-C6H4N=NC6H4-S) 2 (1), two bridging ligands, 1,4-C6H4(tpy)2 (3) and 1,3,5-C6H3(C・C-tpy)3 (4), and metal ions. The quantitative complexation of the ligands and FeII ions was monitored by electrochemical measurements in linear oligomers of 3 up to eight complexation cycles and in branched oligomers of 4 up to four cycles. STM observation of branched oligomers at low surface coverage showed an even distribution of nanodots having uniform size and shape, suggesting the quantitative formation of dendritic structures.The electron transport mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential step chronoamperometry (PSCA). The unique i-t behavior, obtained similarly in all conditions indicates that electron conduction occurs not by diffusional motion but by successive electron hopping between neighboring redox sites within a molecular wire. This is the first observation of redox conduction in a single molecular wire in redox polymer films.Other studies such as fabrication of Co-Ru wires and anthraquinone-bridged metal complex molecular wires were also reported.We also constructed a ferrocenylabozenezene SAM which can undergo reversible isomerization with a single green light source and a redox reaction.