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衍生物通过其分子结构可能表现出明显不同的性质和/或功能，因为它们的形状与单体TTF衍生物的基本平坦性质完全不同。之前，我们制备了TTF二聚体，其中两个TTF部分平行保持或通过四个亚烷基二硫链正交，它们的电结晶得到具有独特电子和/或磁性的复合物。在本研究中，已经尝试制备两种（线性和环状）柔性供体主体。它们由三到四个 TTF 部分组成，可以通过“诱导配合”与大型三维受体（如富勒烯）形成超分子组装体。其中中心 TTF 部分通过两个丙二硫基团连接到两个标记 TTF 的线性类型已成功实现准备好了。两个受保护的硫醇基团位于两端，可以很容易地转化为各种官能团。然而，它们的性质还有待研究。相反，亚乙基二硫代同系物很难制备，主要是由于中间体的溶解度低。由四个TTF组成的大环的制备，其中4-和5-C都连接已尝试通过丙二基基团与相应的加盖 TTF 部分。使用标准亚磷酸三烷基酯方案对相应的 1,3-二硫醇-2-酮/硫酮环状四聚体进行四重 TTF 偶联，即使在存在大量过量的对应分子的情况下，也仅得到不充分偶联的产物。制备与亚丙基二硫基或亚乙基二硫基连接的类似环状三聚体的努力也没有成功。目前已经尝试了连接预制的三个TTF的新途径。已制备出线性 TTF 三聚体前体，并对其成环反应进行了详细研究。