Alternatively linking fullerene and conjugated polymers

The stereo‐electronic control over bisadditions of conjugated polymers to fullerene (C 60 ) is explored in the formation of alternating copolymers. The chemistry, resulting configuration, and properties of poly(3‐hexylthiophene)‐ alt ‐C 60 copolymers prepared by either classic pyrrolidine ring formation or an atom transfer radical addition are compared. Both routes result in controlled additions of polymers to C 60 . Extensive macromolecular modeling through PM6 methods indicate that there is no conjugation between P3HT and C 60 in the systems studied. This along with 2D‐NMR, AFM, and photovoltaic characterizations of the materials indicate the importance of the structure of the modified C 60 and the nature of the linking group between C 60 and P3HT segments in determining the morphology of the copolymers in the solid state.