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

我们在1987 - 1988年期间对该项目进行了研究。（1）利用~ 1H-NMR和~ 1C-NMR以及氧化还原电位研究了环状二、三、四方杯烯的双（叔丁基硫代）衍生物之间的电子结构差异<13>。结果表明，每个杯烯单元的极化程度几乎相同，而不管杯烯单元的数量。(2)在电子体系中引入一些大体积基团，使电子结构发生显著变化。现在，蒽醌的1，2，3-位被叔丁基或三甲基硅基取代，被合成。在光照射下，蒽醌化合物发生价态异构化反应，生成相应的半杜瓦型蒽醌化合物。该反应具有光化学可逆性和定量性，因此作为一种新型的光致变色体系具有很大的应用前景。同时，时间分辨光谱研究表明，光化学反应是通过最低激发的sinlet和triglet进行的。(3)由于1，3-二硫杂环戊烯[n]具有新颖的氧化还原体系和电致变色性能，有望成为新型电致变色材料的可靠组分。此外，通过对三（噻吨-9-亚基）环丙烷二价阳离子盐和五（1.3-苯并二硫醇-2-亚基）环戊烷与DDQ、TCNQF_4等形成的电荷转移（CT）络合物盐的磁性研究，表明奇数径烯有可能作为电荷转移（CT）络合物型有机铁磁体的给体组分。

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.