Direct Synthesis of Chain-end-functionalized Poly(3-hexylthiophene) without Protecting Groups Using a Zincate Complex

Abstract

Chain-end-functionalized poly(3-hexylthiophene)s (P3HTs) with benzyl alcohol (─PhCH₂ OH), phenol (─PhOH), and benzoic acid (─PhCOOH) groups are directly synthesized based on the Negishi catalyst-transfer polycondensation method utilizing the zincate complex of ^t Bu₄ ZnLi₂ . In this system, neither protection nor deprotection steps are required, and also providing a living polymerization system to control the molecular weight while maintaining a low molar mass dispersity (Ð_M ) of the obtained P3HT derivatives. Indeed, the chain-end-functionalized P3HTs can be synthesized along with controlled number-average molecular weights (M_n = 5100-20 000), low Ð_M (1.06-1.14), and high chain-end functionality (Fn = 46-86%). The Fn values for the alcohol and phenol groups are found to be high (86% for ─PhCH₂ OH and 71% for ─PhOH based on ¹ H NMR, respectively), as also confirmed by matrix-assisted laser desorption/ionization time of flight mass spectroscopy. The easily synthesizable chain-end-functionalized P3HTs will be applicable for the facile synthesis of block and branched polymers containing P3HT as well as its related semiconducting polymer segments.

Keywords: block copolymers; catalyst transfer polycondensation; chain-end functionalization; controlled synthesis; π-conjugated polymers.