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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<jats:sub>2<\/jats:sub>(bis{imidazo\u2010phenanthrolin\u20102\u2010yl}\u2010hydroquinone)(ppy)<jats:sub>4<\/jats:sub>]<jats:sup>2+<\/jats:sup> (1<jats:sup>2+<\/jats:sup>) complex by leveraging both ligand\u2010centered redox property and intramolecular H\u2010bonding for exploring dual excited\u2010state proton\u2010transfer assisted PCET process. The vital role of covalently placed hydroquinone in bridged ligand is investigated as electron\u2013proton transfer (ET\u2010PT) 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 (<jats:sup>3<\/jats:sup>CS<jats:sub>Phen\u2010Im<\/jats:sub>) state of 1<jats:sup>2+<\/jats:sup> with methyl viologen via favorably concerted\u2010PCET pathway. The result indicates strong donor\u2013acceptors coupling, which limits charge recombination and enhances catalytic efficiency. To showcase the potential application, this bioinspired PCET\u2010based 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\u2010dependent endocytosis), better safety profile, and higher photoinduced antiproliferative activity of 1<jats:sup>2+<\/jats:sup> compared to Cisplatin, as explored in 3D tumor spheroids, this study anticipates it to be a potential lead compound.<\/jats:p>","DOI":"10.1002\/smll.202408437","type":"journal-article","created":{"date-parts":[[2024,12,23]],"date-time":"2024-12-23T09:18:56Z","timestamp":1734945536000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["Exploring Excited\u2010State Intramolecular Proton\u2010Coupled Electron Transfer in Dinuclear Ir(III)\u2010Complex via Covalently Tagged Hydroquinone: Phototherapy Through Futile Redox Cycling"],"prefix":"10.1002","volume":"21","author":[{"given":"Maniklal","family":"Shee","sequence":"first","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology  Kharagpur West Bengal 721302 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Julia","family":"Schleisiek","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Biochemistry Ruhr\u2010University Bochum  Universit\u00e4tsstrasse 150 44780 Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nishith","family":"Maity","sequence":"additional","affiliation":[{"name":"Universit\u00e9 Paris\u2010Saclay  CNRS, Institut des Sciences Mol\u00e9cu\u2010laires d'Orsay Orsay 91405 France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gourav","family":"Das","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology  Kharagpur West Bengal 721302 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nicol\u00e1s","family":"Montesdeoca","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Biochemistry Ruhr\u2010University Bochum  Universit\u00e4tsstrasse 150 44780 Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Minh\u2010Huong","family":"Ha\u2010Thi","sequence":"additional","affiliation":[{"name":"Universit\u00e9 Paris\u2010Saclay  CNRS, Institut des Sciences Mol\u00e9cu\u2010laires d'Orsay Orsay 91405 France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kiran R.","family":"Gore","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology  Kharagpur West Bengal 721302 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Johannes","family":"Karges","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Biochemistry Ruhr\u2010University Bochum  Universit\u00e4tsstrasse 150 44780 Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6806-9774","authenticated-orcid":false,"given":"N. 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