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）合成了通过不同长度的寡烯（苯二烯烯烯）接头连接的分子三脚架特三世二五脚架二五脚架二元组及其单层的合成。三脚架具有刚性的阿甘坦核心，将三个CH_2SH腿连接到，以便在金表面上进行化学吸附。这些二元组的自组装单层是在AU（111）表面制备的，并通过电化学测量进行了分析。无论连接器的长度如何，单层的表面密度都被证明是恒定的，这表明邻近的苯茂铁单元是由于Adamantane和线性接头的刚性框架而固定的，具有均匀的分子间距离。还表明，相邻的二循环单位之间的相互作用可忽略不计。这表明每个腓新次单位都与邻近分子保持独立，这表明这些二元组具有潜在用作分子记忆。2）合成扩展的分子三脚架及其单层新的Adamantane Tripod，具有C（CH_3）2SH组，代替CH_2SH组，已合成CH__2SH组。由于两个甲基的膨大，每个三脚架分子都将占据增加的面积，从而导致更大的分子距离。新三硫醇的AU（111）表面上的自组装单层的还原解吸实验表明，分子距离比没有甲基的距离明显宽（10.9 a）。该新三脚架和功能分子单元的二元组的未来合成将使大型功能分子的单层形成