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

: 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 (ÐM ) of the obtained P3HT derivatives. Indeed, the chain-end-functionalized P3HTs can be synthesized along with controlled number-average molecular weights (Mn = 5100-20 000), low ÐM (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.