Impact of backbone linkage positions on the molecular aggregation behavior of polymer photovoltaic materials

It is imperative to advance the structural design of conjugated materials to achieve a practical impact on the performance of photovoltaic devices. However, the effect of the linkage positions (meta-, para-) of the backbone on the molecular packing has been relatively little explored. In this study, we have synthesized two wide-bandgap polymer photovoltaic materials from identical monomers with different linkage positions, using dibenzo[c,h][2,6]-naphthyridine-5,11-(6H,12H)-dione (DBND) as the building block. This study shows that the para-connected polymer exhibits an unexpected 0.2 eV higher ionization potential and a resultant higher open-circuit voltage than the meta-connected counterpart. We found that different linkage positions result in different intermolecular binding energies and molecular aggregation conformations, leading to different HOMO energy levels and photovoltaic performances. Specifically, theoretical calculations and 2D-NMR indicate that P(p-DBND-f-2T) performs a segregated stacking of f-2T and DBND units, while P(m-DBND-f-2T) films form π-overlaps between f-2T and DBND. These results show that linkage position adjustment on the polymeric backbone exerts a profound influence on the molecular aggregation of the materials. Also, the effect of isomerism on the polymer backbone is crucial in designing polymer structures for photovoltaic applications.