"Development of Intrinsically Conductivepi-Conjugated Polymers Containing Multi-stage Redox System"

一曰：内禀导电大分子（ICM）具有极小的禁带宽度，是发展分子器件的基础材料之一。我们设计了新型的ICM候选单体，一系列由芳香杂环和非经典的噻吩与吡嗪-二氢吡嗪氧化还原体系组成的混合三聚体。这些化合物的氧化形式与还原形式和相关低聚物相比具有低得多的光学和电化学能隙。特别是吡咯衍生物具有最低的能隙值（在2100 nm [-0.6eV]处观察到吸收边）在寡杂环化合物中。吡咯衍生物的阳极氧化得到的电活性聚合物表现出一个消失的小电化学能隙。为了建立我们系统的带隙控制的一般策略，我们还研究了定义明确的模型低聚物的结构-性质关系。 ...更多信息 ”串联“和“多功能”ICM将是构建在分子水平上操作的单分子电子器件的主要组件。我们已经开发了一种新的合成方法，以“精确定义”的共轭高度低聚物与低HOMO-LUMO分离。我们已经获得了一系列低能隙的α-六-和α-spetithiophene构成的各种杂环的基础上。3：我们已经开发了一个新的候选系统的分子导线具有一个中心的导电核包围的绝缘体的绝缘体地幔。关键的杂环是3 ′ 4 ′- [N，N ′：N，N ′-双（1，1，4，4，-四甲基-1，4-二硅杂四亚甲基）二（氨基）]-2，2 ′：5 ′，2 ″-三噻吩1。该分子在中心噻吩环的β-位具有大体积基团。一般来说，这种庞大的取代基将阻止共面链构象。然而，所有的实验数据支持在1的整个分子上的高度π-共辄。理论计算表明，1的中心环上的刚性和庞大的取代基包围相邻的噻吩环和稳定的共面链构象。少

1 : Intrinsically conductive macromolecules (ICM), possessing a vanishingly small bandgap, is one of the fundamental materials for the development of molecular devices. We have designed novel candidate monomers for ICM ; a series of mixed trimers composed of aromatic heterocycles and a nonclassical thiophene with pyrazine-dihydropyrazine redox system. The oxidized forms of these compounds have much lower optical and electrochemical energy gaps compared to the reduced forms and the related oligomers. Especially the pyrrole derivative possesses the lowest energy gap value (the absorption edge were observed at 2100nm [-0.6eV]) in oligoheterocycles reported so far. The anodic oxidation of the pyrrole derivative gave the electroactive polymer exhibiting a vanishingly small electrochemical energy gap. In order to establish general stategies for bandgap controlling of our systems, we have also investigated the structure-properties relationship of the well-defined model oligomers.2 : "Well-def … More ined" and "multifunctional" ICM's will be the main components to construct unimolecular electronic devices operating at the molecular level. We have developed a new synthetic approach to "precisely-defined" conjugated highly oligomers with low HOMO-LUMO separation. We have obtained a series of low energy-gap alpha-sexi-and alpha-spetithiophenes constituted of various heterocycles based on this method.3 : We have developed a new candidate system for molecular wire which have a central conducting core surrounded by an insulator by an insulator mantle. The key heterocycle is 3'4'- [N,N' : N,N'-bis (1,1,4,4, -tetramethyl-1,4-disilatetramethylene) di (amino)] -2,2' : 5', 2"-terthiophene 1. This molecule has bulky groups at the beta-positions of the central thiophene ring. In general such bulky substituents will prevent the coplanar chain-conformations. However, all the experimental data supported a high degree of pi-conjugation over the whole molecule of 1. The theoretical calculations suggest that the rigid and bulky substituents on the central ring of 1 surround the adjacent thiophene rings and stabilize the coplanar chain-conformation. Less