Development of New Organic Materials with Photochromic or Electro-Chromic Function

具有光致变色或电致变色功能的新型有机材料的开发

基本信息

批准号：
63850171
负责人：
YOSHIDA Zen-ichi
金额：
$ 7.23万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research
财政年份：
1988
资助国家：
日本
起止时间：
1988 至 1989
项目状态：
已结题

项目摘要

This research has been carried out with aim of developing both multi-color organic electrochromic systems and highly sensitive photochromic systems by use of novel pi conjugated compounds. The newly prepared tetrakis(4-hydroxyphenyl)thienothiophene and 1,3-dithiole- radialenes and dendralenes constructed reversible redox systems with their corresponding oxidized species, and vivid three color change was observed. Anthraquinone was chosen as a fundamental molecular skeleton for photochromic molecule, because of its intrinsic spectral sensitivity at long wavelength region as well as its resistibility toward photo-degradation. We employed steric strain, which forces bending of the aromatic ring in a vibrational mode operative for photochemical formation of valence isomers such as Dewar and valene isomers. Thus, 1,2,3-tri-t-butyl anthraquinone was synthesized. Comparing to the electronic spectrum of the parent molecule, the spectrum of 1,2,3-tri-t-butylanthraquinone was characteristic having a longest absorption band with a large extinction coefficient of 3500. The bathochromic shift of the band is also notable, and its absorption cut-off reaches to ca. 550 nm. Upon irradiation, the molecule undergoes reversible valence isomerizations between the corresponding hemi-Dewar anthraquinone derivative. The substitutional modification was employed in naphthacenequinone in order to improve spectitral sensitivity. 1,2,3-tri-t-butylnaphthacenequinone gave the corresponding hemi-Dewar isomer, whereas the 7,8,9-tri-t-butyl system gave the valene isomer. Both the photochemical isomerizations was reversible and quantitative. These new photochromic systems would be practically of practical use.

本研究的目的是利用新型π共轭化合物开发多色有机电致变色系统和高灵敏度光致变色系统。新制备的四(4-羟基苯基)噻吩并噻吩与1,3-二硫杂环烯和树枝烯与其相应的氧化物质构建了可逆氧化还原体系，并观察到鲜艳的三色变化。蒽醌被选为光致变色分子的基本分子骨架，因为它在长波长区域具有固有的光谱敏感性以及对光降解的抵抗力。我们采用了空间应变，它迫使芳香环以振动模式弯曲，从而可光化学形成杜瓦瓶和瓦烯异构体等化合价异构体。由此，合成1,2,3-三叔丁基蒽醌。与母体分子的电子光谱相比，1,2,3-三叔丁基蒽醌的光谱特征是具有最长的吸收带，消光系数高达3500。该带的红移也很显着，并且其吸收截止值达到约。 550纳米。辐射后，分子在相应的半杜瓦蒽醌衍生物之间发生可逆的价异构化。对并四苯醌进行取代修饰以提高光谱灵敏度。 1,2,3-三叔丁基并四苯醌得到相应的半杜瓦异构体，而7,8,9-三叔丁基系统得到瓦烯异构体。两种光化学异构化都是可逆且定量的。这些新的光致变色系统将具有实际用途。