Enhancement of singlet oxygen generation based on incorporation of oxoporphyrinogen (OxP) into microporous solids
Enhancement of singlet oxygen generation based on incorporation of oxoporphyrinogen (OxP) into microporous solids
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DOI：
10.1016/j.mtchem.2021.100534
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发表时间：
2021-08
影响因子：
7.3
通讯作者：
J. Hynek;D. Payne;M. Chahal;F. Sciortino;Y. Matsushita;L. Shrestha;K. Ariga;J. Labuta;Y. Yamauchi;J.P. Hill
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文献类型：
--
作者：
J. Hynek;D. Payne;M. Chahal;F. Sciortino;Y. Matsushita;L. Shrestha;K. Ariga;J. Labuta;Y. Yamauchi;J.P. Hill
产生单线态氧1 O2的化合物对于光动力疗法或有机氧化转化非常有用。本文报道了一系列含氧卟啉原的多孔配位聚合物的合成及其光化学性能。氧化卟啉原，以前未报道的一类单线态氧发生器来自氧化的抗氧化剂取代的卟啉四（3，5-二叔丁基-4-羟基苯基）卟啉，转化为分子tectons通过引入oligophenylene-carboxylate连接体，并纳入到多孔的配位聚合物使用众所周知的oxo-Zr（IV）6簇化学。分析了它们的结构和质地性质，揭示了最佳连接基长度（联苯基）的高达650 m2 g − 1的实质性表面积。氧代卟啉原前体表现出良好的单线态氧生成量子产率（高达Φ = 0.37），并且所得配位聚合物保持了高水平的活性，其在单线态氧生成方面似乎上级前体和报道的参考材料。将这些OxP-PCP材料应用于硫化物选择性氧化为亚砜。这项工作表明，优秀的单线态氧发生器oxoporphyrinogens可以成功地纳入多孔固体和方便地应用于多相氧化转化。
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)6cluster chemistry. Their structures and textural properties were analyzed revealing substantial surface areas up to 650 m2g−1for 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. TheseOxP-PCPmaterials 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.