Angular-Shaped 4,9-Dialkyl - and -Naphthodithiophene-Based Donor-Acceptor Copolymers: Investigation of Isomeric Structural Effects on Molecular Properties and Performance of Field-Effect Transistors and Photovoltaics

Two angular-shaped 4,9-didodecyl -aNDT and 4,9-didodecyl -aNDT isomeric structures have been regiospecifically designed and synthesized. The distannylated -aNDT and -aNDT monomers are copolymerized with the Br-DTNT monomer by the Stille coupling to furnish two isomeric copolymers, PNDTDTNT and PNDTDTNT, respectively. The geometric shape and coplanarity of the isomeric -aNDT and -aNDT segments in the polymers play a decisive role in determining their macroscopic device performance. Theoretical calculations show that PNDTDTNT possesses more linear polymeric backbone and higher coplanarity than PNDTDTNT. The less curved conjugated main chain facilitates stronger intermolecular - interactions, resulting in more redshifted absorption spectra of PNDTDTNT in both solution and thin film compared to the PNDTDTNT counterpart. 2D wide-angle X-ray diffraction analysis reveals that PNDTDTNT has more ordered -stacking and lamellar stacking than PNDTDTNT as a result of the lesser curvature of the PNDTDTNT backbone. Consistently, PNDTDTNT exhibits a greater field effect transistor hole mobility of 0.214 cm(2) V-1 s(-1) than PNDTDTNT with a mobility of 0.038 cm(2) V-1 s(-1). More significantly, the solar cell device incorporating the PNDTDTNT:PC71BM blend delivers a superior power conversion efficiency (PCE) of 8.01% that outperforms the PNDTDTNT:PC71BM-based device with a moderate PCE of 3.6%.