End-group stannylation of regioregular poly(3-hexylthiophene)s

Mono- and bis-stannylation at the chain ends of regioregular poly(3-hexylthiophene) (P3HT) were conducted by post-functionalization of P3HT synthesized through Ni-catalyzed Grignard metathesis polymerization. Lithiation of P3HT with s-BuLi and subsequent stannylation with Me3SnCl led to the formation of bis-stannylated P3HT. The highest conversion of 81% was achieved with the additive N,N,N′,N′-tetramethylethylenediamine (TMEDA), which could enhance the stability of the lithiated compound. On the other hand, mono-stannylated P3HT was synthesized without contamination by bis-stannylated P3HT through successive reactions with a Grignard reagent and Me3SnCl.