Cyclometalating Ligand Affords NIR Absorption in Ruthenium Complexes for Type‐I Photodynamic Therapy
Angewandte Chemie International Edition, vol. 64, pp. e202512296
Abstract
Abstract The development of NIR photosensitizers (PSs) based on Ru complexes with Type‐I process holds substantial promise for photodynamic therapy (PDT) of cancer, though this breakthrough remains unrealized to date. Herein, a pair of cyclometalated Ru enantiomers, [Λ/Δ‐Ru‐dqpy‐TPABP]Cl (dqpy: 2,6‐di(quinolin‐2‐yl)pyridine; TPABP: 4‐(4‐(pyridine‐2‐yl)‐2,1,3‐benzothiadiazol‐7‐yl)triphenylamine) (Λ/Δ‐Ru‐TPABP), were synthesized and evaluated. These complexes exhibit strong Ru(d) and TPABP(π) → dqpy(π*) charge transfer ((metal and ligand)–ligand charge transfer; ML–LCT) absorption at ∼640 nm, with an extended absorption tail reaching up to 800 nm. Moreover, the TPABP ligand, with its strong electron‐rich capacity, contributes to T 1 formation, which increases the electron transfer possibility in the triplet state and promotes Type‐I PDT, making it highly effective for killing cancer cells under hypoxic conditions. Further encapsulating Λ/Δ‐Ru‐TPABP into polymeric nanoparticles results in high tumor inhibition efficiency (>85%) and causes a strong tumoricidal effect and inhibits lung metastasis of breast tumors under 700 nm light irradiation, thus offering a new strategy for developing NIR Ru complexes for anticancer treatment through the design of cyclometalating ligand.
Authors 10
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Dalian University of Technology · State Key Laboratory of Fine Chemicals
Affiliation as printed
State Key Laboratory of Fine Chemicals Frontiers Science Center for Smart Materials Oriented Chemical Engineering Dalian University of Technology Dalian 116024 China
Both authors contributed equally to this work
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
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Xiaolong Zeng Aachen DWI - Leibniz Institute for Interactive Materials Institute of Technical and Macromolecular Chemistry
Dalian University of Technology · DWI – Leibniz Institute for Interactive Materials · State Key Laboratory of Fine Chemicals · RWTH Aachen University
Affiliation as printed
DWI‐Leibniz Institute for Interactive Materials & Institute of Technical and Macromolecular Chemistry RWTH Aachen University 52074 Aachen Germany
State Key Laboratory of Fine Chemicals Frontiers Science Center for Smart Materials Oriented Chemical Engineering Dalian University of Technology Dalian 116024 China
Both authors contributed equally to this work
DWI‐Leibniz Institute for Interactive Materials & Institute of Technical and Macromolecular Chemistry RWTH Aachen University 52074 Aachen Germany
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
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Dalian University of Technology · State Key Laboratory of Fine Chemicals
Affiliation as printed
State Key Laboratory of Fine Chemicals Frontiers Science Center for Smart Materials Oriented Chemical Engineering Dalian University of Technology Dalian 116024 China
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
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Dalian University of Technology · State Key Laboratory of Fine Chemicals
Affiliation as printed
State Key Laboratory of Fine Chemicals Frontiers Science Center for Smart Materials Oriented Chemical Engineering Dalian University of Technology Dalian 116024 China
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
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Dalian University of Technology · State Key Laboratory of Fine Chemicals
Affiliation as printed
State Key Laboratory of Fine Chemicals Frontiers Science Center for Smart Materials Oriented Chemical Engineering Dalian University of Technology Dalian 116024 China
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
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Dalian University of Technology · State Key Laboratory of Fine Chemicals
Affiliation as printed
State Key Laboratory of Fine Chemicals Frontiers Science Center for Smart Materials Oriented Chemical Engineering Dalian University of Technology Dalian 116024 China
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
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Dalian University of Technology · State Key Laboratory of Fine Chemicals
Affiliation as printed
State Key Laboratory of Fine Chemicals Frontiers Science Center for Smart Materials Oriented Chemical Engineering Dalian University of Technology Dalian 116024 China
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
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Dalian University of Technology · State Key Laboratory of Fine Chemicals
Affiliation as printed
Liaoning Binhai Laboratory Dalian 116023 China
Ningbo Institute of Dalian University of Technology Ningbo 315016 China
State Key Laboratory of Fine Chemicals Frontiers Science Center for Smart Materials Oriented Chemical Engineering Dalian University of Technology Dalian 116024 China
Liaoning Binhai Laboratory, Dalian, 116023 China
Ningbo Institute of Dalian University of Technology, Ningbo, 315016 China
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
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Dalian University of Technology · State Key Laboratory of Fine Chemicals
Affiliation as printed
Liaoning Binhai Laboratory Dalian 116023 China
State Key Laboratory of Fine Chemicals Frontiers Science Center for Smart Materials Oriented Chemical Engineering Dalian University of Technology Dalian 116024 China
Liaoning Binhai Laboratory, Dalian, 116023 China
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
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Wen Ce Sun corresponding
Dalian University of Technology · State Key Laboratory of Fine Chemicals
Affiliation as printed
Liaoning Binhai Laboratory Dalian 116023 China
Ningbo Institute of Dalian University of Technology Ningbo 315016 China
State Key Laboratory of Fine Chemicals Frontiers Science Center for Smart Materials Oriented Chemical Engineering Dalian University of Technology Dalian 116024 China
Liaoning Binhai Laboratory, Dalian, 116023 China
Ningbo Institute of Dalian University of Technology, Ningbo, 315016 China
State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, Dalian University of Technology, Dalian, 116024 China
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