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Synthesis, Properties and Fundion of Cage-shaped Oligothiophenes

笼状低聚噻吩的合成、性质及基础

基本信息

批准号：
18550034
负责人：
KURATA Hiroyuki
金额：
$ 2.57万
依托单位：
Osaka 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

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18550034/
关键词：
cage-molecule thiophene oligothiophene silane Sonogashira coupling acetylene X-ray analysis diacetylene Sonogashiraカップリング

项目摘要

Unfortunately, we could not obtain the target compounds, which is cage molecules contsracted with oligothiophene chains, we prepared a cage compound bridged with diacetylene units, a precursor of the target, and got several new findings during the synthetic studuies.The most bothering feauture is a unexpected high reactivity of bond between silicon and carbon on thiophen ring. To functionalize thiophene rings of tris (2-thienyl) silane derivatives, the selection of the fourth substituent on the silicon atom is important. Sterically hindered substituent is requared for protection of carbon-silicon bond from reactants. We found that isobutyl group is bearable to some reactions, but it is still nessesary for searching better substituent.The cage compound bridged with diacetylene units is prepared by Pd-catalyzed oxidative coupling of triethynyl derivative, though the yield was low. The structure of the compound was determined by X-ray crystallography. In crystal, it has C3 symmetry, propably due to the long carbon-silicon bond. Furthermore, the UV-Vis and fluorescence spectra reflect the effect of silicon atom. While significant bathochromic shift was not observed by comparison with non-caged analoge, absorption coefficients were remarkably increased. Relatively strong fluorescent was shown on the cage compound.

不幸的是，我们无法得到与低聚硫吩链相连的笼状分子，我们制备了一个与目标的前体二乙炔单元桥联的笼状化合物，并在合成研究中得到了几个新的发现。最令人不安的特征是硫吩环上硅和碳之间出人意料的高反应活性。要使三(2-噻吩基)硅烷衍生物的噻吩环功能化，硅原子上第四取代基的选择是很重要的。为了保护碳-硅键不受反应物的影响，需要空间受阻的取代基。我们发现异丁基对某些反应是可以接受的，但对于寻找更好的取代基仍然是必要的。通过钯催化氧化偶联三乙炔基衍生物制备了桥联二乙炔单元的笼形化合物，但产率较低。用X-射线单晶衍射法确定了该化合物的结构。在晶体中，它具有C3对称性，可能是由于长的碳-硅键。此外，紫外-可见光谱和荧光光谱也反映了硅原子的影响。与非笼形类似物相比，红移不明显，但吸收系数显著增加。笼状化合物显示出较强的荧光。