Polymerization strategies for poly(triarylamine)s via Buchwald–Hartwig amination

Poly(triarylamine)s (PTAAs) are widely employed as hole‐transporting materials in organic electronic and optoelectronic devices, including organic field‐effect transistors, organic light‐emitting diodes, and perovskite solar cells. However, their synthesis has historically been limited by the modest yields and narrow substrate scope associated with copper‐mediated Ullmann condensation. Although palladium‐catalyzed Suzuki–Miyaura coupling offers a versatile alternative to overcome these limitations, the multistep preparation of monomers remains a significant drawback. In contrast, Buchwald–Hartwig amination has emerged as a powerful synthetic platform for the construction of PTAAs from readily accessible building blocks. In this review, we systematically examine various Buchwald–Hartwig amination‐based synthetic approaches for producing structurally diverse PTAA materials and discuss how each strategy governs the structural precision and molecular architecture of the resulting materials.