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Highly Selective Detection of Hypochlorous Acid by a Bis-heteroleptic Ru(II) Complex of Pyridyl-1,2,3-triazole Ligand via C(sp2)–H Hydroxylation

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journal contribution
posted on 24.07.2019, 18:33 by Bhaskar Sen, Sanjoy Kumar Sheet, Sumit Kumar Patra, Debaprasad Koner, Nirmalendu Saha, Snehadrinarayan Khatua
A Ru­(II) complex (Ru-1) of a substituted pyridyl-1,2,3-triazole ligand (BtPT) for highly selective “light-up” detection of hypochlorous acid is presented. An unusual anti-Markovnikov HOCl addition to the CC bond of 1,2,3-triazole and a highly specific C­(sp2)–H hydroxylation over epoxidation made Ru-1 a highly selective luminescent HOCl probe. The abnormal regio- and stereoselective HOCl addition and subsequent hydroxylation mechanism in detail is supported by the combination of ESI-MS, 1H/13C NMR spectroscopy, and 1H NMR titration. The hydroxylation at the C5 center in 1,2,3-triazole increases the electron density and makes BtPT a better σ-donor as well as π-donor, which in turn increases the 3MC–3MLCT energy gap and inhibits the nonradiative decay from the excited state of Ru-1 and is the key reason for luminescence light-up. Most importantly, the exogenous and endogenous HOCl imaging in the living HEK293T cells is also demonstrated. The probe showed low cytotoxicity and efficiently permeated the cell membrane. The cell-imaging experiments revealed rapid staining of the extranuclear region of HEK293T cells which clearly indicates the presence of cytoplasmic HOCl. The endogenous HOCl generation and imaging, stimulated by lipopolysaccharides (LPS) and paraquat in the HEK293T cells, is also demonstrated.