Synthesis of Poly(3-hexylthiophene) with a Narrower Polydispersity

The polymerization of 2‐bromo‐3‐hexyl‐5‐iodothiophene (1) with isopropylmagnesium chloride and Ni(dppp)Cl2 was quenched with 5 M hydrochloric acid instead of water to yield head‐to‐tail poly(3‐hexylthiophene) (HT‐P3HT) with a very low polydispersity. The $\overline M _{\rm n}$ of the polymer was controlled by the feed ratio of 1 to Ni(dppp)Cl2. Quenching with 5 M hydrochloric acid seemed to promote protonolysis of HT‐P3HT‐Ni complexes before the coupling reaction between HT‐P3HT. GPC profiles of HT‐P3HT obtained after quenching with water and 5 M hydrochloric acid, respectively.