title: Gadolinium(III) Porpholactones as Efficient and Robust Singlet Oxygen Photosensitizers.
abstract: Construction of Gd(III) photosensitizers is important for designing theranostic agents owing to the unique properties arising from seven unpaired f electrons of the Gd(3+) ion. Combining these with the advantages of porpholactones with tunable NIR absorption, we herein report the synthesis of Gd(III) complexes Gd-1-4 (1, porphyrin; 2, porpholactone; 3 and 4, cis- and trans-porphodilactone, respectively) and investigated their function as singlet oxygen ((1) O2 ) photosensitizers. These Gd complexes displayed (1) O2 quantum yields (ΦΔ s) from 0.64-0.99 with the order Gd-1<Gd-2<Gd-3<Gd-4. The gradually enhanced (1) O2 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 (1) Δg →(3) Σg transition of (1) O2 . 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 Gd(III) 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.
authors.affiliation: 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, 100871, P.R. China.
authors.forename: Xian-Sheng
authors.initials: XS
authors.lastname: Ke
authors.affiliation: 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, 100871, P.R. China.
authors.forename: Yingying
authors.initials: Y
authors.lastname: Ning
authors.affiliation: 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, 100871, P.R. China.
authors.forename: Juan
authors.initials: J
authors.lastname: Tang
authors.affiliation: 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, 100871, P.R. China.
authors.forename: Ji-Yun
authors.initials: JY
authors.lastname: Hu
authors.affiliation: 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, 100871, P.R. China.
authors.forename: Hao-Yan
authors.initials: HY
authors.lastname: Yin
authors.affiliation: 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, 100871, P.R. China.
authors.forename: Gao-Xiang
authors.initials: GX
authors.lastname: Wang
authors.affiliation: 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, 100871, P.R. China.
authors.forename: Zi-Shu
authors.initials: ZS
authors.lastname: Yang
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P.R. China.
authors.forename: Jialong
authors.initials: J
authors.lastname: Jie
authors.affiliation: College of Chemistry, Beijing Normal University, Beijing, 100875, P.R. China.
authors.forename: Kunhui
authors.initials: K
authors.lastname: Liu
authors.affiliation: 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, 100871, P.R. China.
authors.forename: Zhao-Sha
authors.initials: ZS
authors.lastname: Meng
authors.affiliation: Department of Chemistry, Renmin University of China, Beijing, 100872, P.R. China.
authors.forename: Zongyao
authors.initials: Z
authors.lastname: Zhang
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P.R. China.|College of Chemistry, Beijing Normal University, Beijing, 100875, P.R. China.
authors.forename: Hongmei
authors.initials: H
authors.lastname: Su
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
authors.forename: Chunying
authors.initials: C
authors.lastname: Shu
authors.affiliation: 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, 100871, P.R. China. zhangjunlong@pku.edu.cn.
authors.forename: Jun-Long
authors.initials: JL
authors.lastname: Zhang
keywords: gadolinium; photocatalysis; photocytotoxicity; singlet oxygen; tetrapyrrole