Side Chain Structure Affects the Photovoltaic Performance of Two-Dimensional Conjugated Polymers

We used Stille coupling of electron-rich benzo[1,2-b:4,5-b′]dithiophene (BDT) presenting conjugated alkylthiophene (T), alkylphenyl (P), or alkylfuran (F) side chains with electron-deficient alkoxy-modified 2,1,3-benzooxadiazole (BO) moieties to obtain a series of two-dimensional, conjugated, D−π–A polymers (PBDTTBO, PBDTPBO, and PBDTFBO). The side chains of the BDT units altered the solubility, conformations, and electronic properties of the synthesized conjugated polymers, allowing tuning of their photovoltaic properties when blended with fullerenes. Density functional theory calculations revealed that the presence of these side chain groups on the BDT donor units affected the torsion angles between the side chain groups and the conjugated main chains but resulted in only slightly different energy levels for the highest occupied molecular orbitals for these polymers, consistent with results obtained experimentally using cyclic voltammetry. These polymers displayed excellent thermal stabilities (5 wt % d...