Synthesis and Properties of Novel Non-planar Extended Quinonoid Molecules Having o-Quinonoid Structure

点击翻译按钮获取中文摘要

Our research results are summarized as follows.1.Synthesis and properties of the extended pyracyloquinone derivativeThe extended-quinone derivativeof cyclopenta[fg]acenaphthylene-1, 2-dione (pyracyloquinone) was first synthesized and characterized. The molecular structure determined by X-ray analysis and redox behavior reflect the antiaromatic characted of the pyracylene moiety.2.Synthesis and properties of novel redox system having dithieno snnelsted bis(spirodienone) skeletonIn the course of the synthetic study on thioindigo-extended quinones, we prepared bis(benzo[b]thiophene)-annelated dispiro[5.4.5.0]hexadeca-1,4,7,9,12,15-hexaene-3,14-dione, a new skeleton molecule. This compound showed a ring-opening trasformation by two-electron reduction, and a photo-responsive property detected by ESR spectroscopy. Furthermore, a novel quaterquinone derivative based on dithieno-annelated dispiro[5.4.5.0]hexadeca-1,4,7,9,12,15-hexaene-3,14-dione was synthesized, which is a dark-green crystalline substance with metallic luster, shows a srtong absorption at 675nm. The temperature dependency of the redox process was elucidated by cyclic voltammetry.3.Synthesis of dithieno annelated o-terphenoquinone derivativesNovel o-terphenoquinone derivatives having benzo[2,1-b : 3,4-b']dithiophene and benzo[1,2-b : 4,3-b']dithiophene skeletons were synthesized from the correspondig bisphenols, prepared by McMurry coupling of the diketone derivatives. These quinones exist as the equiblibium mixture of the quinone-form and the diradical-form. Further oxidation of them afforded another speaces having deep-red and deep-blue color respectively. Detailed study of these compouds are in progress.