Structural studies of poly(dimethyl-tetrathiophene, an intermediate between poly(thiophene) and poly(3-methylthiophene)

Abstract Grignard coupling of 2-bromo-3-methylthiophene and 5,5′-dibromo-2,2′-dithiophene, and chemical polymerization of the resulting tetramer using FeCl 3 as coupling agent gave a new type of substituted polythiophene, namely Poly(3,3‴-dimethyl-(2,2′:5′,2′:5′,2‴)tetrathiophene)) (PDMTT), with two new and interesting features compared to conventional polythiophenes. Firstly, we have a polythiophene with exact methyl side group positioning, eliminating the possibility of side group position disorder. Secondly, and especially interesting from a structural point of view, we obtained a polymer which is intermediate between the unsubstituted polythiophene (PT) and poly(3-methylthiophene) (P3MT). The polymer was obtained as a black insoluble powder which turned out to be amorphous. X-ray diffraction profiles were measured and compared to the profiles of PT and P3MT. We were able to follow the intensity and position variation of the diffraction peaks as a function of the methyl substitution.