尽管二维共价有机骨架（2D COF）中普遍存在六边形、四边形和三角形孔结构，但五边形孔仍然明显不存在。我们在此提出了开罗五边形镶嵌 COF，这是通过精确选择连接器的几何形状和度量来实现的，从而产生了前所未有的 mcm 拓扑。在每个五边形结构中，卟啉单元在 15.5 Å 周围形成 90° 角的四个均匀侧面，而四联苯单元则在 11.6 Å 左右形成 120° 角的底边，与开罗五角大楼的标准精确对齐。根据窄带隙和强近红外（NIR）吸光度，合成的COF表现出高效的单线态氧（1O2）生成和光热转换，从而实现近红外光热联合光动力治疗以引导癌细胞凋亡。机制研究表明，良好的 1O2 生成能力可上调细胞内脂质过氧化，导致谷胱甘肽耗竭、谷胱甘肽过氧化物酶 4 低表达并诱导铁死亡。这项工作中五边形开罗镶嵌的实施为采用新拓扑以及多模式近红外光疗的 COF 多样化提供了一种有前景的策略。© 2024。作者。

Despite the prevalent of hexagonal, tetragonal, and triangular pore structures in two-dimensional covalent organic frameworks (2D COFs), the pentagonal pores remain conspicuously absent. We herein present the Cairo pentagonal tessellated COFs, achieved through precisely chosen geometry and metrics of the linkers, resulting in unprecedented mcm topology. In each pentagonal structure, porphyrin units create four uniform sides around 15.5 Å with 90° angles, while tetrabiphenyl unit establish a bottom edge about 11.6 Å with 120° angles, aligning precisely with the criteria of Cairo Pentagon. According to the narrow bandgap and strong near-infrared (NIR) absorbance, as-synthesized COFs exhibit the efficient singlet oxygen (1O2) generation and photothermal conversion, resulting in NIR photothermal combined photodynamic therapy to guide cancer cell apoptosis. Mechanistic studies reveal that the good 1O2 production capability upregulates intracellular lipid peroxidation, leading to glutathione depletion, low expression of glutathione peroxidase 4, and induction of ferroptosis. The implementation of pentagonal Cairo tessellations in this work provides a promising strategy for diversifying COFs with new topologies, along with multimodal NIR phototherapy.© 2024. The Author(s).