Singlet oxygen, ¹O₂, generating compounds are highly useful for photodynamic therapy or organic oxidative transformations. In this work, the synthesis and photochemical performances for singlet oxygen generation of a range of oxoporphyrinogen-containing porous coordination polymers (OxP-PCPs) are reported. Oxoporphyrinogens, a previously unreported class of singlet oxygen generators derived from the oxidation of the antioxidant-substituted porphyrin tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl)porphyrin, were converted to molecular tectons by the introduction of oligophenylene-carboxylate linkers and incorporated into porous coordination polymers using well-known oxo-Zr(IV)₆ cluster chemistry. Their structures and textural properties were analyzed revealing substantial surface areas up to 650 m² g⁻¹ for the optimum linker length (biphenylyl). The oxoporphyrinogen precursors exhibit good quantum yields of singlet oxygen generation (up to Φ = 0.37), and a high level of activity is maintained in the resulting coordination polymers, which appear to be superior for singlet oxygen generation to the precursors and to a reported reference material. These OxP-PCP materials were applied for the selective oxidation of sulfides to sulfoxides. This work demonstrates that the excellent singlet oxygen generator oxoporphyrinogens can be successfully incorporated as porous solids and conveniently applied in heterogeneous oxidative transformations.

单线态氧¹ O ₂生成化合物对于光动力疗法或有机氧化转化非常有用。在这项工作中，报告了一系列含氧卟啉原的多孔配位聚合物 ( OxP-PCP ) 的单线态氧产生的合成和光化学性能。氧卟啉原是一种先前未报道的单线态氧发生器，其源自抗氧化剂取代的卟啉四（3,5-二叔丁基-4-羟基苯基）卟啉的氧化，通过引入低聚苯甲酸酯转化为分子构造连接器并使用众所周知的氧代-Zr(IV) ₆掺入多孔配位聚合物簇化学。对它们的结构和质地特性进行了分析，揭示了对于最佳接头长度（联苯基）而言高达 650 m ²  g ^{-1 的}大量表面积。氧卟啉原前体表现出良好的单线态氧产生量子产率（高达 Φ = 0.37），并且在所得配位聚合物中保持高水平的活性，这似乎优于前体和报道的参考文献的单线态氧产生材料。这些OxP-PCP材料用于将硫化物选择性氧化为亚砜。这项工作表明，优异的单线态氧发生器氧卟啉原可以成功地作为多孔固体并入，并方便地应用于非均相氧化转化。