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

共轭材料由于其物理性质使其成为发射器件和塑料电子器件的理想材料而获得了广泛的重视。其中最吸引人的性质是它们的低氧化电位和光和电化学激发态，为电子器件提供合适的发射。不幸的是，这些所需材料的制备需要严格的反应条件，使用金属催化剂是有问题的去除。此外，用于制备此类材料的耦合方法导致产品不一致，性能不可靠。偶氮亚胺（- n =C-）共聚物是理想的替代品，因为它们不需要严格的反应条件就能形成一致的产物。当使用芳基前体时，生成的键具有抗水解、抗还原和抗氧化性。建议合成含有2或3个共价连接的含有末端胺的噻吩的新型共聚物。这提供了氨基噻吩和噻吩衍生物，可以与各种芳香醛缩合，提供高度共轭的化合物。考虑到噻吩作为共轭聚合物前体的重要性，提出了以2,5-噻吩乙醛为起始原料，采用格瓦尔德反应合成2,2'-二氨基噻吩的方法。提出了噻吩的取代化学反应，以合成各种2,2'-二氨基噻吩衍生物。各种电子给体和撤回基团可以很容易地纳入到3和4的位置，允许微调的物理性质，除了增加溶解度。将进行各种前体与芴和噻吩二醛的缩合反应。提出了所得到的物理性质，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.