Abstract A new phosphafluorene (PF) based monomer, featuring a phosphine oxide substituted with a dodecyl chain, was synthesized. PF was copolymerized with benzodithiophene (BDTT) to form the copolymer PPF-BDTT which has a donor (BDTT)–acceptor (PF) structure. For the first time, direct post-polymerization modifications were performed on the phosphorus center of phosphafluorene-containing conjugated polymers. With Lawesson's Reagent, PPF-BDTT was transformed from a phosphine oxide to a phosphine sulfide. Reduction of the phosphine oxide of PPF-BDTT with HSiCl3, followed by reaction with AuCl∙SMe2, produced PPF-BDTT-Au, which contains AuCl coordinated to the phosphafluorene moiety. PPF-BDTT, PPF-BDTT-S, and PPF-BDTT-Au were characterized optically and electrochemically and the results compared to related BDTT containing copolymers. PPF-BDTT and its derivatives were found to have high LUMO and HOMO levels and larger bandgaps compared to common donor-acceptor copolymers. Organic solar cells were fabricated from PPF-BDTT, PPF-BDTT-S, and PPF-BDTT-Au, although the performances of these devices were poor with power conversion efficiencies ranging from 0.13% to 0.60%.

中文翻译：

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含磷共轭共聚物的聚合后改性

摘要 合成了一种新型磷芴（PF）基单体，其特征是氧化膦被十二烷基链取代。PF与苯并二噻吩（BDTT）共聚形成共聚物PPF-BDTT，该共聚物具有供体（BDTT）-受体（PF）结构。首次对含磷芴共轭聚合物的磷中心进行直接的后聚合改性。使用 Lawesson 试剂，PPF-BDTT 从氧化膦转化为硫化膦。用 HSiCl3 还原 PPF-BDTT 的氧化膦，然后与 AuCl∙SMe2 反应，产生 PPF-BDTT-Au，其中包含与磷芴部分配位的 AuCl。PPF-BDTT、PPF-BDTT-S 和 PPF-BDTT-Au 进行了光学和电化学表征，并将结果与​​相关的含有 BDTT 的共聚物进行了比较。与常见的供体-受体共聚物相比，发现 PPF-BDTT 及其衍生物具有高 LUMO 和 HOMO 能级和更大的带隙。有机太阳能电池由 PPF-BDTT、PPF-BDTT-S 和 PPF-BDTT-Au 制成，尽管这些器件的性能很差，功率转换效率在 0.13% 到 0.60% 之间。