Poly(3-dodecylthienylenevinylene)s: Regioregularity and Crystallinity

A series of poly(dodecylthienylenevinylenes), C 12 -PTVs- a: b, with tunable regioregularity and solubility have been synthesized using two isomeric comonomers with molar ratios from 0:10 to 5:5, and characterized by NMR spectroscopy, differential scanning calorimetry, absorption spectroscopy, cyclovoltammetry, and X-ray diffraction. For the first time, the aromatic and olefinic 1 H NMR peaks of regioregular head–tail C n -PTVs are clearly assigned. No major difference in XRD peak intensity is observed among regiorandom and fully regioregular C 12 -PTVs. V oc of C 12 -PTVs- a: b and PC 60 BM blend solar cells are in the range of 0.43 to 0.51 V and consistently decrease as regioregularity is reduced. C 12 -PTV-3:7:PC 60 BM solar cells give the highest short-circuit current and practically same efficiency as that of C 12 -PTV-1:9:PC 60 BM devices. The results suggest a new strategy to enhance processability of optoelectronic polymers without sacrificing their crystallinity and device performance.