Poly(alkylbithiazoles): A New Class of Variable-Band Gap Conjugated Polymer

高共轭聚合物是很有前途的材料，可以用作电池或传感器的电极，led的发光半导体，以及防腐蚀或防静电涂层。这项研究开启了生产具有可调性能的新聚合物的可能性。柯蒂斯的研究小组最近合成了一类新的共轭聚合物，聚烷基二噻唑（PABTs）。这些新的聚合物具有烷基侧链，使它们可溶于普通有机溶剂，并且可以从这些溶液中铸造薄膜。这些新聚合物是区域规则的，并表现出前所未有的多态性和伴随的多色性。薄膜的溶剂热处理引起固态相变，其特征是共轭长度大幅增加，带隙减小。本研究旨在确定多晶相的结构，并确定聚合物侧链的分子结构如何影响固态包装、相变能量、结晶度、电导率以及光或电致发光效率。将合成模型低聚物，并通过x射线衍射确定其三维结构。这些模型研究将有助于解释高MW聚合物的x射线和EXAFS数据。将聚合物和模型低聚物与各种氧化剂掺杂，并确定掺杂体系的结构和光谱性质（UV-VIS， ESR，磁化率等），并与中性前驱体进行比较。这种结构-性能关系的系统研究将为优化聚合物结构以获得高导电性、高电致发光效率、热稳定性或光稳定性等特定性能提供新的数据。PABTs在链主链上有一个基本的氮官能团，可以烷基化或用于形成金属配合物。这些反应改变了链上的电势。这样的变化可用于改变电导率或作为激子阱以增加发光效率和改变发射光的波长。＊＊＊

9510274 Curtis Highly conjugated polymers are promising materials for use as electrodes in batteries or sensors, as the light-emitting semiconductor in LEDs, and as anti-corrosion or anti-static coatings. This research opens the possibility of producing new polymers with tunable properties. %%% Curtis' research group has recently synthesized a new class of conjugated polymers, the poly(alkylbithiazole)s, PABTs. These new polymers have alkyl side chains that render them soluble in common organic solvents, and thin films may be cast from these solutions. These new polymers are regioregular and show unprecedented polymorphism with attendant polychromism. Thermal of solvent annealing of the films induces solid state phase transformations that are characterized by large increases in the conjugated length and decreases in the band gap. This research seeks to determine the structures of the polymorphic phases and to determine how the molecular structure of the polymer side chains influences the solid-state packing, phase- transformation energetics, crystallinity, conductivity, and photo- or electroluminescence efficiency. Model oligomers will be synthesized and their 3-dimensional structures determined by X-ray diffraction. These model studies will aid the interpretation of X-ray and EXAFS data on the high MW polymers. The polymers and model oligomers will be doped with a variety of oxidants and the structures and spectroscopic properties (UV-VIS, ESR, magnetic susceptibility, etc.) of the doped systems will be determined and compared with the neutral precursors. This systematic study of structure-property relationships will provide new data for optimizing polymer structure for specific properties, e.g. high conductivity, high electroluminescence efficiency, thermal- or photo-stability, etc. The PABTs have a basic nitrogen functional group in the chain backbone that can be alkylated or used to form metal complexes. These reactions alter the potential along the chain. Such changes may be used to alter conductivity or to act as exciton traps to increase luminescence efficiency and alter the wavelength of the emitted light. ***