Poly(3-hexylthiophene) bearing pendant fullerenes: aggregation vs. self-organizationElectronic supplementary information (ESI) available: Detailed synthesis, NMR, UV-Vis, FTIR, PL spectra, XRD, TGA and TEM images. See DOI: 10.1039/b9py00384c

Novel graft copolymers are reported based on poly(3-hexylthiophene) (P3HT) bearing side chains of poly(styrene- stat -chloromethylstyrene), onto which a fullerene C 60 or PCBM is covalently attached. P3HT was brominated at the 4-position to various extents (1-30 mol%), subsequently Suzuki-coupled with the boronic ester of 1-(4′-bromophenyl)-1-(2″,2″,6″,6″-tetramethyl-1-piperidinyloxy)ethyl (tempo) to form a nitroxide-functionalized P3HT macroinitiator, which was then used to initiate the nitroxide-mediated radical polymerization (NMRP) of chloromethylstyrene (CMS)- stat -styrene (ST) side chains. CMS units were functionalized with azide units and used to attach fullerene. The polymers contained a relatively high mass content of fullerene (20-41 wt%). Photoluminescence of P3HT is strongly quenched by the fullerene. The absorption of P3HT maximum shifts toward shorter wavelengths with increasing graft density. Films of PCBM/C 60 graft copolymers form a bicontinuous morphology with feature sizes