Influence of the Substituent and Polymerization Methodology on the Properties of Chiral Poly(dithieno[3,2-b:2‘,3‘-d]pyrrole)s

Abstract

2′,3′-d]pyrrole)s (PDTPs) with high molecular weights, good yields, and increased solubility were prepared, and their supramolecular behavior was studied. The polymers differ in their polymerization method (using chemical oxidants, Stille-couplings, or a Yamamoto-type polymerization) and the bulkiness of the side chain. The solubility of the polymer depends on the bulkiness of the side chains employed, while the yield and, to a lesser extent, the molecular weight depend on the polymerization method. In general, Stille-couplings proved to be the best polymerization method for PDTPs. The higher molecular weight polymers showed more defined voltammograms, higher λ max together with the presence of a vibronic fine-structure, and higher fluorescence yields than lower molecular weight materials. In solution, the polymers are present as highly conjugated rigid rods, which, upon transition to films or in nonsolvents, poorly aggregate. The stacking is more complicated in high molecular weight polymers than in low molecular weight samples.

Direct (hetero)arylation polymerization for the synthesis of donor–acceptor conjugated polymers based on N‐benzoyldithieno [3,2‐b:2′,3′‐d]pyrrole and diketopyrrolopyrrole toward organic photovoltaic cell application

“…No glass transition in this temperature range was detected for PDTDPPHBDP (P1), while relatively broad endotherms attributed to melting transitions at 225 °C were observed for PDTDPPBDP (P2) and PDTDPP0.2BDP0.8HBDP (P3). It is well known that linear conjugated polymers with stiff main chains exhibit very strong intermolecular π–π stacking interactions, resulting in high melting temperatures normally above 200 °C . The DSC result agrees with the XRD result, showing that PDTDPPHBDP (P1) with brush alkyl chains exhibited no melting transition, whereas the melting transitions of the other polymers clearly suggest aggregation of conjugated main chains.…”

Solar cells based on semi-random P3HT analogues containing dithienopyrrole: influence of incorporating a strong donor

“…Recently, a family of polymers containing DPP as the acceptor was synthesized combining not only the advantages of rr-P3HT (high-hole mobility, semi-crystallinity, and good miscibility with PCBM) with a broad and intense absorption profile, but also illustrating the tremendous potential of this new class of polymers with solar cell efficiencies as high as 5%. 20,26,[28][29][30] Additionally, the solubility of the polymer can be tuned through the alkyl substituents on the nitrogen in DTP without a negative influence on the polymer backbone. However the influence of incorporating a small amount of strong donor monomer into the polymer backbone has yet to be studied.…”

Effects of Molecular Structure on Intramolecular Charge Carrier Transport in Dithieno [3,2-b: -d] Pyrrole-Based Conjugated Copolymers

“…The synthetic routes for DTP polymers are shown in Scheme 1. DTP copolymers and DTP homopolymer were prepared by SuzukiMiyaura coupling reaction and Yamamoto-type polymerization, respectively [28,29]. The reaction scheme is displayed in Figure 1.…”