Leone Amanda K, Mueller Emily A, McNeil Anne J
Department of Chemistry and Macromolecular Science and Engineering Program , University of Michigan , 930 North University Avenue , Ann Arbor , Michigan 48109-1055 , United States.
J Am Chem Soc. 2018 Nov 14;140(45):15126-15139. doi: 10.1021/jacs.8b09103. Epub 2018 Nov 1.
Conjugated polymers are the workhorse materials in organic electronics, a field that is rapidly growing to encompass energy storage devices such as supercapacitors and batteries. The highest-performing materials today have incredibly diverse structures and are accessed via step-growth polymerizations. This method results in limited control over the polymer's molecular weight, sequence, and dispersity, all of which can significantly impact device performance. The discovery of catalyst-transfer polymerization (CTP) in 2004 was predicted to change this landscape. Instead, nearly 14 years later, the CTP scope remains mostly limited to polymerizing small, electron-rich monomers. There is a pronounced gap between the rich array of structures utilized in organic electronics and what can be polymerized in a living, chain-growth fashion via CTP. Here, we suggest that palladium precatalysts could bridge this gap based on their huge versatility in the small-molecule cross-coupling literature. We highlight specific ancillary ligands from the small-molecule literature that we anticipate are candidates for enabling diverse conjugated polymer syntheses based on nearly a decade of research into the CTP mechanism. In addition, we describe several recent promising examples of CTP mediated by Pd precatalysts that serve as inspiration for the future. We present this Perspective as a call-to-action to advance organic electronics with CTP.
共轭聚合物是有机电子学中的主力材料，这一领域正在迅速发展，涵盖了诸如超级电容器和电池等储能设备。如今性能最佳的材料具有极其多样的结构，是通过逐步增长聚合反应制备的。这种方法对聚合物的分子量、序列和分散度的控制有限，而所有这些都会对器件性能产生重大影响。2004年催化剂转移聚合（CTP）的发现预计会改变这一局面。然而，近14年后，CTP的适用范围大多仍局限于聚合小的富电子单体。有机电子学中使用的丰富结构阵列与通过CTP以活性链增长方式聚合的结构之间存在明显差距。在此，我们认为钯预催化剂基于其在小分子交叉偶联文献中的巨大通用性，可以弥合这一差距。我们重点介绍了小分子文献中的特定辅助配体，基于对CTP机理近十年的研究，我们预计这些配体是实现多种共轭聚合物合成的候选者。此外，我们描述了几个最近由钯预催化剂介导的CTP的有前景的例子，这些例子为未来提供了灵感。我们提出这一观点，旨在呼吁采取行动，通过CTP推动有机电子学的发展。
