Thèse de doctorat en Matière condensée, chimie et organisation
Sous la direction de Jean-Jacques Aaron.
Soutenue en 2005
à Paris 7 .
Dérivés du thiéno[3,2-b]pyrrole benzofusionné : synthèses et comportement électrochimique et spectral
This thesis deals with the synthesis of novel 1,4-diheteropentalene compounds, especially 4H-thieno[3,2-b]indoles and 1H-benzothieno[3,2-b]pyrrole, and the investigation of their electropolymerization. The aim was to prepare new conducting polymers and to determine how the structure of the monomer influences their electrochemical and spectral properties. The investigation can be subdivided into four parts. 1. In the context of the research on 1,4-diheteropentalenes performed in our laboratory in recent years, I have designed and prepared a series of novel thienoindoles and the isomeric benzothienopyrrole. The known synthetic procedure was extended to the preparation of thienoindoles with various electron-donating substituents in the benzene ring. After several unsuccessful synthetic approaches I found a new synthetic route to the thienoindole core. 2. The compounds synthesized are ideal candidates for the preparation of new conducting polymers which can be obtained by their electropolymerization. This hypotesis has already been proved by the polymerization of structurally related thieno[3,2-b]benzomiophenes. Thus, the second part of my research work has been focused on the electrochemical behaviour of the compounds prepared and on the electrosynthesis of polymers. This research work represents the first attempt to polymerize these 1,4-diheteropentalenes. 3. As a consequence with my research on polymer preparation, I have been also engaged in the investigation of their physicochemical and spectral properties. After the appropriate analyses I found that most of the polymers, obtained as films, are electroactive or conducting and consist of an oligomer mixture. Moreover, several exhibit very interesting spectral properties which designate them for applications in electrochromic devices or polymer-based light-emitting diodes. 4. I have also focused on the relationship between the structure of the monomer and the properties of the polymer. Electron-donating groups introduced into the thienoindole core, as well as the order of the pentalenes in the fused heterocycle, change basically the monomer reactivity towards polymerization, and determine the electroactivity and structure of the products. In addition, electron-donating substituents in the benzene ring of thienoindole have an essential influence on the spectral properties of the polymers.
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