Cathodic Hydrodefluorination of a π-Conjugated Alternating Copolymer Consisting of 9,9-Dioctylfluorene and Tetrafluorophenylene (Supporting Information)

Fluorine-containing π-conjugated polymers show unique optoelectronic properties because of installed fluorine atoms into their main chains. To manipulate their optoelectronic properties, replacing fluorine atoms with other functional groups or elements by polymer reaction is straightforward. However, polymer reactions applicable to fluorine-containing π-conjugated polymers remain limited to those using nucleophilic aromatic substitution reactions. Here, we report the cathodic hydrodefluorination of a 1,2,4,5-tetrafluorophenylene moieties containing π-conjugated polymer using a platinum (Pt) plate or a zinc (Zn) plate as a working electrode. The use of a Pt plate as a working electrode converts tetrafluorophenylene units to difluorophenylene units and monofluorophenylene units. On the other hand, the use of a Zn plate as a working electrode is found to be effective in suppressing the formation of the monofluorophenylene units. We also demonstrate the facile tuning of the optoelectronic properties of the pristine π-conjugated polymer by the cathodic hydrodefluorination.

含氟的π共轭聚合物因其主链中嵌入的氟原子而展现出独特的光电子特性。为了操控其光电子性质，通过聚合物反应替换氟原子以其他官能团或元素的方法简便易行。然而，适用于含氟π共轭聚合物的聚合物反应仍局限于那些使用亲核芳香族取代反应的案例。在本研究中，我们报道了使用铂（Pt）电极或锌（Zn）电极作为工作电极，对含有π共轭的1,2,4,5-四氟苯基片段进行阴极氢脱氟的反应。以铂电极作为工作电极，可将四氟苯基单元转化为二氟苯基单元和单氟苯基单元。另一方面，使用锌电极作为工作电极被发现能有效抑制单氟苯基单元的形成。我们还展示了通过阴极氢脱氟轻松调节原始π共轭聚合物的光电子性质。