Thiophene-Fused 1,10-Phenanthroline and Its Conjugated Polymers

A novel type of π-extended 1,10-phenanthroline, specifically with fused thiophene groups at the less exploited 3-, 4-, 7-, and 8-positions of the phenanthroline ring, and its conjugated polymers were designed and synthesized. The current developed route is based on the Bischler–Napieralski cyclization of the (1,2-phenylene)­diamide precursor, which offers a facile and versatile strategy for preparing soluble and well-defined 1,10-phenanthroline derivatives and their analogues. High molecular weight poly­(phenanthroline-co-fluorene)­s with good solubility in common organic solvents or water were prepared by palladium-catalyzed Suzuki–Miyaura–Schlüter polycondensation. The optical responsive properties of these thiophene-fused 1,10-phenanthroline-containing polymers have demonstrated these polymers could be a good candidate for potential applications as luminescent chemosensor materials thanks to the specific repeating unit along the backbone.本研究设计并合成了一类新型π扩展型1,10-菲咯啉（1,10-phenanthroline）衍生物，其在菲咯啉环较少被开发利用的3、4、7、8位引入了稠合噻吩基团，并制备了对应的共轭聚合物。当前开发的合成路线基于(1,2-亚苯基)二酰胺前体的Bischler–Napieralski环化反应，该路线为制备可溶性、结构明确的1,10-菲咯啉衍生物及其类似物提供了一种简便且通用的策略。通过钯催化的Suzuki–Miyaura–Schlüter缩聚反应，制备了在常见有机溶剂及水中均具有良好溶解性的高分子量聚(菲咯啉-共聚-芴)。对这类含噻吩稠合1,10-菲咯啉单元的聚合物的光学响应性能研究表明，得益于其主链上的特定重复结构单元，该类聚合物可作为发光化学传感材料的优质潜在候选材料。