-Alkylation -alkylation: influence on the performance of the photovoltaic cells based on a tetracyclic lactam polymer donor.

Lactam-containing acceptors, which could provide two potential alkylation positions (-alkylation and -alkylation), are important building blocks for polymeric donors in high performance polymer solar cells (PSCs). However, the influence of alkylation positions on the PSC performance has seldom been studied. Herein, we investigated the influence of -alkylation and -alkylation on a novel bislactam acceptor, namely dibenzonaphthyridinedione (DBND), on the physical properties of the corresponding polymers and hence their PSC performance. Besides -alkylated and -alkylated DBND, half--alkylated-half--alkylated DBND (,-DBND) was also prepared and copolymerized with stannyl bithiophene (2T). It was found that by varying the alkylation positions, the optical, crystalline and aggregation properties of the corresponding polymers were greatly altered. In comparison with P(-DBND-2T) and P(-DBND-2T), P(,-DBND-2T) shows both better solubility and shorter π-π stacking distance. By blending with PCBM, P(,-DBND-2T) forms better nano-fibrillar phase separation so that less charge recombination is observed, thus leading to a much better power conversion efficiency (PCE) around 5%, which is the highest value of the conjugated system based on ,-alkylated acceptors. The results show that the asymmetric ,-alkylation protocol is a promising way to adjust the properties of the bislactam-containing conjugated polymers.