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Development of Novel Photoresponsive Systems Using an Excimer State

使用准分子态开发新型光响应系统

基本信息

批准号：
09450348
负责人：
ITAGAKI Hideyuki
金额：
$ 6.91万
依托单位：
Shizuoka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1999
项目状态：
已结题

项目摘要

We have Shown through the present project that 1,n-bis(3-(1-pyrenyl)propyl-carboxy)-oxaalkanes (DP3n: n= 3 to 6), linear oligooxyethylenes with pyrenyl groups at both ends, captured and transported metal ions more effectively when they were irradiated. Two terminal pyrenyl groups link together to form an excimer when irradiated with uv light, and this structure is analogous to that of crown ethers. Thus, we refer to them as "photo-induced crown ether compounds" (PIC's). It is the first work to use an excimer to fix a conformation of a molecule. In the present work, we proved the concept of PIC by using 8 compounds such as DP3n and 7 metal ions having different sizes, and examined the relationship between the sizes of PIC's and the metal ions captured by them. We employed a quartz cell (1cm × 2.5cm × 7cm high) with a partition to determine the amount of metal ions transported by PIC molecules in the presence and absence of uv light, after a method for measuring transportation yield of metal ions by crown ethers. Consequently, DP35 and DP34 transported the greatest amount. of CaィイD12+ィエD1 and CdィイD12+ィエD1, respectively. We assume that DP3n molecules do not start with capturing metal ions after forming an excimer, but rather they have some interaction with ions before being excited, because some specific interactions were observed through ィイD11ィエD1H-NMR measurements when CaィイD12+ィエD1 and CdィイD12+ィエD1 were added into the solution of DP35 and DP34. The intramolecular excimer formation between the pyrenyl end groups is considered to make PIC's bind metal ions very tightly when irradiated. Finally the novel concept of a photo-induced crown ether compound is successfully established to be correct and useful for developing the photo-responsible system.

我们通过本项目表明，1，n-二(3-(1-吡喃基)丙基-羧基)-氧杂烷烃(DP3n：n=3~6)，即两端带有戊烯基的直链低聚氧乙烯，在辐照下能更有效地捕获和传输金属离子。当紫外光照射时，两个末端的吡喃基团连接在一起形成准分子，这种结构类似于冠醚。因此，我们将它们称为“光诱导冠醚化合物”(PIC‘s)。这是第一个使用准分子来固定分子构象的工作。在本工作中，我们用DP3n等8种化合物和7种不同大小的金属离子证明了PIC的概念，并考察了PIC的大小与它们捕获的金属离子之间的关系。我们采用1 cm×2.5 cm×7 cm高的石英池，在测量冠醚金属离子输运产额的方法后，测定了PIC分子在紫外光存在和不存在的情况下对金属离子的输运量。因此，DP35和DP34的运输量最大。分别为CaィイD12+ィエD 1和CDィイD12+ィエD 1。我们假设DP3n分子不是从形成准分子后捕获金属离子开始的，而是在被激发之前与离子发生了一些相互作用，因为通过ィイD11ィエ的D1H-核磁共振测量，在DP35和DP34的溶液中加入了CaィイD12+ィエD1和CdィイD12+ィエD1时，观察到了一些特殊的相互作用。分子内吡喃基端基团之间的准分子的形成被认为使PIC在辐照时与金属离子结合得非常紧密。最后，成功地建立了光诱导冠醚化合物的新概念，为开发光响应系统提供了正确和有用的信息。