Exploring Excited-State Intramolecular Proton-Coupled Electron Transfer in Dinuclear Ir(III)-Complex via Covalently Tagged Hydroquinone: Phototherapy Through Futile Redox Cycling.

Autor: Shee M; Department of Chemistry, Indian Institute of Technology, Kharagpur, West Bengal, 721302, India., Schleisiek J; Faculty of Chemistry and Biochemistry, Ruhr-University Bochum, Universitätsstrasse 150, 44780, Bochum, Germany., Maity N; Université Paris-Saclay, CNRS, Institut des Sciences Molécu-laires d'Orsay, Orsay, 91405, France., Das G; Department of Chemistry, Indian Institute of Technology, Kharagpur, West Bengal, 721302, India., Montesdeoca N; Faculty of Chemistry and Biochemistry, Ruhr-University Bochum, Universitätsstrasse 150, 44780, Bochum, Germany., Ha-Thi MH; Université Paris-Saclay, CNRS, Institut des Sciences Molécu-laires d'Orsay, Orsay, 91405, France., Gore KR; Department of Chemistry, Indian Institute of Technology, Kharagpur, West Bengal, 721302, India., Karges J; Faculty of Chemistry and Biochemistry, Ruhr-University Bochum, Universitätsstrasse 150, 44780, Bochum, Germany., Singh NDP; Department of Chemistry, Indian Institute of Technology, Kharagpur, West Bengal, 721302, India.
Jazyk: angličtina
Zdroj: Small (Weinheim an der Bergstrasse, Germany) [Small] 2024 Dec 23, pp. e2408437. Date of Electronic Publication: 2024 Dec 23.
DOI: 10.1002/smll.202408437
Abstrakt: Anticipating intramolecular excited-state proton-coupled electron transfer (PCET) process within dinuclear Ir 2 -photocatalytic system via the covalent linkage is seminal, yet challenging. Indeed, the development of various dinuclear complexes is also promising for studying integral photophysics and facilitating applications in catalysis or biology. Herein, this study reports dinuclear [Ir 2 (bis{imidazo-phenanthrolin-2-yl}-hydroquinone)(ppy) 4 ] 2+ (1 2+ ) complex by leveraging both ligand-centered redox property and intramolecular H-bonding for exploring dual excited-state proton-transfer assisted PCET process. The vital role of covalently placed hydroquinone in bridged ligand is investigated as electron-proton transfer (ET-PT) mediator in intramolecular PCET and validated from triplet spin density plot. Moreover, bimolecular photoinduced ET reaction is studied in acetonitrile/water medium, forging the lowest energy triplet charge separated ( 3 CS Phen-Im ) state of 1 2+ with methyl viologen via favorably concerted-PCET pathway. The result indicates strong donor-acceptors coupling, which limits charge recombination and enhances catalytic efficiency. To showcase the potential application, this bioinspired PCET-based photocatalytic platform is studied for phototherapeutics, indicating significant mitochondrial localization and leading to programmed cell death (apoptosis) through futile redox cycling. Indeed, the consequences of effective internalization (via energy-dependent endocytosis), better safety profile, and higher photoinduced antiproliferative activity of 1 2+ compared to Cisplatin, as explored in 3D tumor spheroids, this study anticipates it to be a potential lead compound.
(© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)
Databáze: MEDLINE
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