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Development of Ordered Monolayer Based on the Self Assembly of Molecular Tripods

基于分子三脚架自组装的有序单分子层的发展

基本信息

批准号：
18550124
负责人：
KITAGAWA Toshikazu
金额：
$ 2.64万
依托单位：
Mie University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

项目摘要

1) Synthesis of Molecular Tripod-Ferrocene Dyads and Their MonolayersDyads consisting of a molecular tripod and ferrocene, connected through oligo (phenyleneethynylene) linkers of different lengths, were synthesized. The tripod has a rigid adamantane core to which three CH_2SH legs are attached in order to enable chemisorption on gold surface. The self-assembled monolayers of these dyads were prepared on Au (111) surface and analyzed by means of electrochemical measurements. The surface densities of the monolayers were shown to be constant irrespective of the length of the linker, demonstrating that the adjacent ferrocene units are fixed with a uniform intermolecular distance due to the rigid framework of adamantane and linear linker. It was also shown that there is negligible interaction among neighboring ferrocene units. This indicates that each ferrocene unit is kept independent from adjacent molecules, suggesting that these dyads are of potential use as molecular memories.2) Synthesis of an Extended Molecular Tripod and Its MonolayerA new adamantane tripod, having C(CH_3)2SH groups in place of the CH_2SH groups, was synthesized. Owing to the bulkiness of the two methyl groups, each tripod molecule is expected to occupy an increased area, resulting in greater molecular distance. Reductive desorption experiments for the self-assembled monolayer on Au(111) surface of this new trithiol showed that the molecular distance is significantly wider(10.9 A) than without the methyl groups. Future synthesis of dyads of this new tripod and functional molecular units would enable formation of monolayers of large-sized functional molecules

1)分子三角架-二茂铁二联体及其单分子膜的合成合成由分子三角架和二茂铁组成的二联体，通过不同长度的低聚（苯撑乙炔基）连接体连接。三脚架有一个刚性金刚烷核，三个CH_2SH腿连接到金表面上，以使化学吸附。在Au（111）表面上制备了这两种二联体的自组装单分子膜，并通过电化学方法进行了分析。的单层的表面密度被证明是恒定的，而不管连接器的长度，表明相邻的二茂铁单元是固定的具有均匀的分子间距离，由于金刚烷和线性连接器的刚性框架。研究还表明，相邻的二茂铁单元之间的相互作用可以忽略不计。这表明每个二茂铁单元与相邻的分子保持独立，表明这些二联体作为分子记忆体具有潜在的用途。2）扩展的分子三脚架及其单层的合成了一种新的金刚烷三脚架，其CH_2SH基团被C（CH_3）_2SH基团取代。由于两个甲基的庞大性，预期每个三脚架分子占据增加的面积，导致更大的分子距离。还原脱附实验表明，该三硫醇分子在Au（111）表面的自组装单层膜的分子间距比不含甲基时明显增大（10.9 A）。这种新的三脚架和功能分子单元的二联体的未来合成将能够形成大尺寸功能分子的单层