Two-dimensional conjugated polymers (2DCPs), composed of multiple strands of linear conjugated polymers with extended in-plane π-conjugation, are emerging crystalline semiconducting polymers for organic (opto)electronics. They are represented by two-dimensional π-conjugated covalent organic frameworks, which typically suffer from poor π-conjugation and thus low charge carrier mobilities. Here we overcome this limitation by demonstrating two semiconducting phthalocyanine-based poly(benzimidazobenzophenanthroline)-ladder-type 2DCPs (2DCP-MPc, with M = Cu or Ni), which are constructed from octaaminophthalocyaninato metal(ii) and naphthalenetetracarboxylic dianhydride by polycondensation under solvothermal conditions. The 2DCP-MPcs exhibit optical bandgaps of ~1.3 eV with highly delocalized π-electrons. Density functional theory calculations unveil strongly dispersive energy bands with small electron–hole reduced effective masses of ~0.15m₀ for the layer-stacked 2DCP-MPcs. Terahertz spectroscopy reveals the band transport of Drude-type free carriers in 2DCP-MPcs with exceptionally high sum mobility of electrons and holes of ~970 cm² V⁻¹ s⁻¹ at room temperature, surpassing that of the reported linear conjugated polymers and 2DCPs. This work highlights the critical role of effective conjugation in enhancing the charge transport properties of 2DCPs and the great potential of high-mobility 2DCPs for future (opto)electronics.

二维共轭聚合物 (2DCP) 由多股具有扩展面内 π 共轭的线性共轭聚合物组成，是用于有机（光）电子学的新兴结晶半导体聚合物。它们以二维 π 共轭共价有机框架为代表，通常存在较差的 π 共轭，因此载流子迁移率较低。在这里，我们通过展示两种基于半导体酞菁的聚（苯并咪唑并苯并菲咯啉）梯型2DCP（2DCP-MPc，其中M = Cu或Ni）克服了这一限制，它们是由八氨基酞菁金属（ ii ）和萘四甲酸二酐在溶剂热下通过缩聚构建的。状况。 2DCP-MPc 的光学带隙约为 1.3 eV，具有高度离域的 π 电子。密度泛函理论计算揭示了层堆叠 2DCP-MPc 的强色散能带，小电子空穴减少了约 0.15 m ₀的有效质量。太赫兹光谱揭示了 2DCP-MPc 中 Drude 型自由载流子的能带传输，室温下电子和空穴的总迁移率极高，约为 970 cm ² V ^-1 s ^-1 ，超过了已报道的线性共轭聚合物和 2DCP 。这项工作强调了有效共轭在增强 2DCP 电荷传输特性方面的关键作用以及高迁移率 2DCP 在未来（光）电子学中的巨大潜力。