Preparation of TTF-bsed Oligomeric Donor Hosts with Flexible Structure

具有柔性结构的基于 TTF 的寡聚供体宿主的制备

基本信息

批准号：
16550026
负责人：
KAWADA Yuzo
金额：
$ 2.3万
依托单位：
Ibaraki University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2006
项目状态：
已结题

项目摘要

Three-dimensionally assembled TTF derivatives through their molecular architecture may exhibit markedly different properties and/or functions due to their totally different shapes from the basically flat nature of monomeric TTF derivatives.. Previously we prepared TTF dimer in which two TTF moieties are held either parallel or orthogonal through four alkylenedithio chains and their electrocrystallization gave complexes of unique electronic and/or magnetic properties.In the present study, preparation of two kinds (linear and cyclic) of flexible donor hosts has been tried. They are made of three to four TTF moieties and may form supramolecular assemblies with large three-dimensional acceptors like fullerene through "induced fit".Linear types in which the central TTF moiety is connected to the two franking TTF's through two propylenedithio groups have been successfully prepared. Two protected thiol groups are' located at both of the ends and can be easily converted to various functionalities. Their properties are, however, yet to be studied.. To the contrary, the ethylenedithio homologues are difficult to prepare, mainly due to low solubilitys of intermediates.Preparation of a macrocycle composed of four TTF's whose 4-and 5-C are both connected with a respective franking TTF moiety through propylenditho group have been tried. Quadruple TTF-forming couplings of the corresponding 1,3-dithiole-2-one/thione cyclic tetramer using standard trialkyl phosphite protocols gave only insufficiently coupled products even under the presence of a large excess of the counterpart molecule. Efforts to prepare a similar cyclic trimer connected with propylenedithio or ethylenedithio group have been also unsuccessful.Presently a new route to connect preformed three TTF's has been tried. A linear TTF trimer precursor have been prepared and its ring-forming reaction have been under scrutiny..

三维组装的TTF衍生物通过其分子体系结构可能显示出明显不同的属性和/或功能，这是由于它们与单体TTF衍生物的基本平坦性质完全不同的形状而产生的。以前，我们准备了TTF二聚体，其中两个TTF二聚体具有两个TTF部分，使两个TTF由四个ttf Memioties保持平行或四个磁性电磁和磁性电磁和它们的电气化且它们的电气化且它们的电气环境和它们的电气化元素或磁性电磁，并且它们的电气环境或磁性电磁层及其电源或磁性含量。在本研究中，已经尝试了柔性供体宿主的两种（线性和环状）的制备。它们由三到四个TTF部分制成，并可能通过“诱导的拟合”类型形成具有大型三维受体（如富勒烯）的超分子组件。中央TTF部分通过两个PropylenenedIthio组连接到两个Franking TTF的线性类型，已成功制定。两个受保护的硫醇基团均位于两端，并且可以轻松地转换为各种功能。但是，它们的特性尚未被研究。相反，主要由于中间体的溶解度较低，难以准备。使用标准试验二磷酸盐协议的相应1,3-二二二二二二二酮/thione环四聚体的四倍体TTF形成耦合，即使在大量过量的对应物分子的情况下，即使存在很大的耦合产物。准备与Propylenedithio或Ethylenedithio组相关的类似循环三聚体的努力也没有成功。已经制备了线性TTF三聚体前体，其环形反应受到了审查。