Gadolinium(III) Porpholactones as Efficient and Robust Singlet Oxygen Photosensitizers |
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Authors: | Dr Xian‐Sheng Ke Yingying Ning Juan Tang Ji‐Yun Hu Hao‐Yan Yin Gao‐Xiang Wang Zi‐Shu Yang Jialong Jie Dr Kunhui Liu Dr Zhao‐Sha Meng Zongyao Zhang Prof?Dr Hongmei Su Prof?Dr Chunying Shu Prof?Dr Jun‐Long Zhang |
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Institution: | 1. Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, P.R. China;2. Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, P.R. China;3. College of Chemistry, Beijing Normal University, Beijing, P.R. China;4. Department of Chemistry, Renmin University of China, Beijing, P.R. China;5. Beijing National Laboratory for Molecular Sciences, Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing, P. R. China |
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Abstract: | Construction of GdIII photosensitizers is important for designing theranostic agents owing to the unique properties arising from seven unpaired f electrons of the Gd3+ ion. Combining these with the advantages of porpholactones with tunable NIR absorption, we herein report the synthesis of GdIII complexes Gd‐1 – 4 ( 1 , porphyrin; 2 , porpholactone; 3 and 4 , cis‐ and trans‐porphodilactone, respectively) and investigated their function as singlet oxygen (1O2) photosensitizers. These Gd complexes displayed 1O2 quantum yields (ΦΔs) from 0.64–0.99 with the order Gd‐1 < Gd‐2 < Gd‐3 < Gd‐4 . The gradually enhanced 1O2 sensitization after β‐oxazolone moiety replacement was ascribed to the narrowing of the energy gap (ΔE) between the lowest triplet states (T1) of the ligand and the energy level of the 1Δg→3Σg transition of 1O2. In particular, Gd‐4 is capable of excitation in the visible to NIR region (400–700 nm) with a quantum yield near unity. These Gd complexes were first demonstrated as efficient photosensitizers in photocatalysis such as oxidative C?H bond functionalization of secondary or tertiary amines, and the oxygenation of the natural product cholesterol. Finally, after glycosylation, these water‐soluble Gd complexes showed potential applications in photodynamic therapy (PDT) in HeLa cells. This work revealed that GdIII complexes of “bioinspired” β‐modified porpholactones are efficient NIR photosensitizers and form a chemical basis to construct appealing photocatalysts and theranostic agents based on lanthanides. |
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Keywords: | gadolinium photocatalysis photocytotoxicity singlet oxygen tetrapyrrole |
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