SYNTHESIS OF PI-CONJUGATED POLYMERS WITH RIGIDLY LINEAR STRUCTURES AND ELECTRONIC AND OPTICAL FUNCTIONALITIES BY ORGANOMETALLIC POLYCONDENSATION

我们以镍和钯的配合物为原料，通过有机金属缩聚反应制备了刚性线型π共轭聚合物。这些π共轭聚合物掺杂后具有导电性，并表现出电化学活性和发光性能。合成的聚合物含有由嘧啶并吡啶、吡啶、3，4-亚乙二氧基噻吩和嘧啶组成的聚芳烃S和聚芳亚乙叉S。我们揭示了它们的光致发光、电导和电化学响应，以及它们在固体中的分子间相互作用和堆积结构源于刚性线性结构。光谱和粉末X射线衍射法给出了聚合物的基本信息。π共轭聚合物通常是光致发光的，有时还会表现出电致发光。聚合物由于其刚性的线性结构而具有高粘度，并且在拉伸的薄膜中表现出强烈的二向色性。在聚合过程中，强烈建议形成中间体有机镍钯络合物。我们制备了中间体的模型化合物，并对其分子结构进行了分析，得到的π共轭聚合物由于分子间相互作用在固体中呈p2gg或面对面聚集堆积结构，堆积方式影响发光效率。聚合物的易氧化和易还原反映了重复单元的基本电子性质。

We have prepared rigidly linear π-conjugated polymers by organometallic polycondensation using nickel and palladium complexes. These π-conjugated polymers were electrically conductive after doping, and showed electrochemically active and luminescent properties. The synthesized polymers contain poly(arylene)s and poly(aryleneethynylene)s composed of pyrimidopyridine, pyridopyradine, 3,4-ethylenedioxythiophene, and pyrimidine. We have revealed their photoluminescent, electrically conducting, and electrochemical responses, as well as their intermolecular interaction and packing structure in the solid originated from the rigidly linear structure. Spectroscopy and powder X-ray diffraction methods gave fundamental information about the polymers.The π-conjugated polymers are usually photoluminescent and sometimes show electroluminescence. The polymers give a high viscosity due to their rigidly linear structure and exhibit a strong dichroism in stretched films. In the course of the polymerization, formation of intermediate organo-nickel and-palladium complexes is strongly suggested. We prepared model compounds for the intermediates and analyzed their molecular structure.The obtained π-conjugated polymers take p2gg or face-to-face aggregated packing structure in the solid due to the intermolecular interaction, and the packing mode influenced efficiency of the luminescence. The ease of oxidation and reduction of the polymers reflect the basic electronic properties of the repeating units.