Synthesis and Physical Properties of New Electron Systems having a Novel Electronic Structure

具有新颖电子结构的新型电子系统的合成和物理性质

基本信息

批准号：
62470085
负责人：
YOSHIDA Zen-ichi
金额：
$ 5.06万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1987
资助国家：
日本
起止时间：
1987 至 1988
项目状态：
已结题

项目摘要

We have performed our research with the titled project for the period of 1987 - 1988. The following results were obtained:(1) The defference of electronic structure between bis(tert-butylthio) derivatives of cyclic bi-, tri-, and tetra-calicenes was investigated on the basis of ^1H- and ^<13>C-NMR, and redox potential results. It was shown that each calicene unit polarizes in almost the same degree irrespectively of the number of calicene units.(2) Introduction of some bulky groups into electron systems, provides remarkable change in their electronic structures. Now, anthraquinones substituted with tert-butyl or trimethylsilyl groups at the 1, 2, and 3-positions, were synthesized. Under photoirradiation the anthraquinones were subjected to valence isomerization into the corresponding hemi-Dewar types of anthraquinones. This reaction is photochemically reversible and quantitaltive, thus bringing much expectation as a new type of photochromic system. Also, time-resolved spectrometric study demonstrated that the photochemical reaction proceeds via lowest excited sinlet and triglet.(3) Since 1,3-dithiole[n]radialenes construct a novel redox system and exhibit electrochromism, they can be expected as reliable component for a new type of electrochromic material. Furthermore, the odd-numbered radialenes were shown to have a possibility of a donor component for the production of a charge-transfer (CT) complex type of prganic ferromagnet, from the investigation on the magnetic properties of tris(thioxanthen-9-ylidene)cyclopropane dication salt and CT complex salts of pentakis(1.3-benzodithiol-2-ylidene)cyclopentane with DDQ and TCNQF_4 etc.

我们已经通过1987年至1988年的标题项目进行了研究。（1）基于 ^1H-和 ^<13> c-nmr的 ^1H--和 ^<13> c-nmr和redox的潜在结果，研究了环环，三 - 和四核烯之间的双（tert-butylthio）衍生物之间的电子结构的脱附。结果表明，每个钙烯单元在几乎相同的程度上偏振钙元单位的数量。（2）将某些笨重的基团引入电子系统中，其电子结构可显着变化。现在，合成了用1、2和3位的Tert丁基或三甲基甲硅烷基类取代的蒽醌。在光照射下，将蒽喹酮对相应的半乳腺类型的蒽喹酮类型进行价异构化。该反应在光化学上是可逆的和定量的，因此带来了新型的光致变色系统的期望。同样，时间分辨的光谱研究表明，光化学反应是通过最低激发的罪行和触发器进行的。（3）自从1,3-二硫代[n] radialenes构建了一种新型的氧化还原系统并表现出电化色素，因此它们可以作为一种新型的电染色体材料作为可靠的成分作为可靠的成分。此外，从研究Tris（Thioxanthen-9-基因）环丙烷盐和CT复合盐的磁性特性的研究中，奇数径向径向径向有可能产生供体成分，以生产供电 - 转移（CT）复杂类型的Pranganic Feromagnet。 pentakis（1.3-苯并二硫醇-2-甲基）带有DDQ和TCNQF_4的环烷烷基