Conjugated ladder polymers (CLPs) are difficult yet captivating synthetic targets due to their fully unsaturated fused backbones. Inherent challenges associated with their synthesis often lead to low yields, structural defects, and insoluble products. Here a new method to form CLPs is demonstrated, utilizing a high-yielding dimerization of annulated zirconacyclopentadienes to form cyclooctatetraene (COT) monomer units. The resulting COT-containing polymers form rapidly in a single ladderization step from the bis-zirconacyclopentadiene precursors and display molecular weights up to 29.7 kDa. The polymers represent rare examples of CLPs with negatively curved rings, resulting in the observation of unusual properties. The rigid tub-shaped COT units embedded in the backbone imbue the polymers with microporosity, exhibiting BET surface areas up to 555 m2/g. Additionally, the remarkable solubility of these CLPs in organic solvents enables the fabrication of thin films showcasing high dielectric performance with a discharged energy density as high as 6.54 J/cm3 at 650 MV/m.

中文翻译：

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从环状双锆环戊二烯直接阶梯化含环八四烯的可加工共轭梯形聚合物


共轭梯形聚合物 （CLP） 由于其完全不饱和的熔融主链，是难以理解但极具吸引力的合成靶标。与其合成相关的固有挑战通常会导致低产率、结构缺陷和不溶性产物。这里展示了一种形成 CLP 的新方法，利用环状锆环戊二烯的高产率二聚化形成环八烯 （COT） 单体单元。所得含 COT 的聚合物在一次阶梯化步骤中从双锆环戊二烯前驱体快速形成，分子量高达 29.7 kDa。聚合物代表了具有负弯曲环的 CLP 的罕见例子，从而观察到不寻常的特性。嵌入主链中的刚性桶状 COT 单元使聚合物具有微孔性，BET 表面积高达 555 m2/g。此外，这些 CLP 在有机溶剂中的显着溶解性使薄膜能够制造出具有高介电性能的薄膜，在 650 MV/m 时的放电能量密度高达 6.54 J/cm3。