Rodríguez-Camargo Andrés, Yildiz Erdost, Juela Diego, Fischer Felix Richard, Graf Daniel, Rath Bibhuti Bhusan, Ochsenfeld Christian, Bauer Matthias, Sitti Metin, Yao Liang, Lotsch Bettina V
Nanochemistry Department, Max Planck Institute for Solid State Research, Heisenbergstraße 1, 70569 Stuttgart, Germany.
Department of Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany.
J Am Chem Soc. 2025 Sep 17;147(37):33472-33481. doi: 10.1021/jacs.5c07787. Epub 2025 Sep 8.
Covalent organic frameworks (COFs) have been emerging as versatile reticular materials due to their tunable structures and functionalities, enabled by precise molecular engineering at the atomic level. While the integration of multiple components into COFs has substantially expanded their structural complexity, the strategic engineering of diverse functionalities within a single framework the random distribution of linkers with varying lengths remains largely unexplored. Here, we report a series of highly crystalline mixed-length multivariate COFs synthesized using azobenzene and bipyridine as linkers, where tuning the ratio of linkers and incorporating palladium effectively modulates the balance between near-infrared (NIR) light absorption and catalytic sites for NIR-generation of hydrogen peroxide (HO). Capitalizing on the deep tissue penetration of NIR light and the generated HO as reactive oxygen species, as a proof of concept, the optimal mixed-length multivariate COF reduces breast cancer cell viability by almost 90% after 1 h of irradiation in a combined photodynamic therapy and drug delivery.
共价有机框架（COFs）由于其可调节的结构和功能，通过原子水平上精确的分子工程实现，已成为多功能的网状材料。虽然将多种组分整合到COFs中极大地扩展了其结构复杂性，但在单个框架内对多种功能进行战略工程设计——具有不同长度的连接体的随机分布在很大程度上仍未被探索。在此，我们报告了一系列使用偶氮苯和联吡啶作为连接体合成的高度结晶的混合长度多变量COFs，其中调节连接体的比例并引入钯有效地调节了近红外（NIR）光吸收与用于近红外光催化生成过氧化氢（HO）的催化位点之间的平衡。利用近红外光的深层组织穿透性以及所生成的HO作为活性氧，作为概念验证，在联合光动力疗法和药物递送中，最佳的混合长度多变量COF在照射1小时后可使乳腺癌细胞活力降低近90%。
