Preparation and characterization of novel azomethine comonomers prepared from conjugated aminothiophene comonomers

共轭材料因其物理性质而获得了广泛的重要性，使其成为发射器件和塑料电子产品的理想材料。其中最吸引人的特性是它们的低氧化电位以及为电子器件提供合适发射的光和电化学激发态。不幸的是，这些所需材料的制备需要使用金属催化剂的严格反应条件，而金属催化剂很难去除。此外，用于制备此类材料的耦合方法导致不一致的产品，具有不可靠的性能。偶氮亚胺(-N=C-)共单体是理想的替代品，因为它们在没有严格的反应条件的情况下很容易形成，产物形成一致。当使用芳基前体时，生成的键具有水解性、还原性和抗氧化性。合成了含有2个或3个含末端胺的共价连接的噻吩类新型共聚单体。这提供了可以与各种芳香醛缩合得到高度共轭化合物的氨基二硫吩衍生物和三噻吩衍生物。鉴于噻吩酮作为共轭聚合物前驱体的重要性，提出了以2，5-噻吩甲醛为起始原料，通过Gewald反应合成2，2‘-二氨基三噻吩环的方法。提出了合成各种2，2‘-二氨基三噻吩衍生物的方法--噻吩基取代化学。不同的电子给体和退出基团可以很容易地结合到3位和4位上，从而除了增加溶解度之外，还可以微调物理性质。将继续进行各种前体与荧烯和噻吩二醛的缩合反应。得到的物理性质包括氧化还原电位、荧光量子产率、激发态寿命、阳极电聚合和光谱电化学。

Conjugated materials have gained a wide importance because of their physical properties making them ideal for emitting devices and plastic electronics. Among the most attractive properties are their low oxidation potentials and photo- and electrochemically excited states affording suitable emissions for electronic devices. Unfortunately, the preparation of these desired materials requires stringent reaction conditions using metal catalysts that are problematic to remove. Furthermore, the coupling methods used to prepare such materials lead to inconsistent products with unreliable properties. Azomethines (-N=C-) comonomers are ideal alternatives because they are easily formed without stringent reaction conditions with consistent product formation. When using aryl precursors, the resulting bond is hydrolytically, reductively, and oxidatively resistant. What is proposed is the synthesis of novel comonomers containing 2 or 3 covalently linked thiophenes containing terminal amines. This affords amino bithiophene and terthiophene derivatives that can be condensed with various aromatic aldehydes affording highly conjugated compounds. Given the importance of thiophene as a precursor for conjugated polymers, the synthesis of 2,2'-diaminoterthiophene is proposed using the Gewald reaction starting from 2,5-thiophene carbaldehyde. The well established substitution chemistry of thiophene is proposed to synthesize various 2,2'-diaminoterthiophene derivatives. Various electron donors and withdrawing groups can be easily incorporated into the 3 and 4 positions allowing the fine tuning of the physical properties in addition to increasing the solubility. The condensation of the various precursors with fluorene and thiophene dialdehydes will be pursued. The resulting physical properties including the redox potentials, fluorescence quantum yields, the excited state lifetimes, anodic electropolymerization, and spectroelectrochemistry are proposed.