Recognition and mechanistic investigation of anion sensing by ruthenium() arene complexes and bio-imaging application

• Published in: Dalton transactions : an international journal of inorganic chemistry 2022-08, Vol.51 (34), p.1371-1384
• Main Authors: Sonkar, Chanchal, Sarkar, Sayantan, Malviya, Novina, Kuznetsov, Maxim L, Mukhopadhyay, Suman
• Format: Article
• Language: English
• Subjects: Anions; Biocompatibility; Ethanol; Fluorescence; Glycine; Hydrogen bonds; Imaging; NMR; Nuclear magnetic resonance; Ruthenium compounds
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d2dt01726a

In this work, four new ruthenium complexes [Ru(η 6 - p -cymene)(L1)Cl] 1 , [Ru(η 6 - p -cymene)(L2)Cl] 2 , [Ru(η 6 - p -cymene)(L3)Cl] 3 and [Ru(η 6 - p -cymene)(L4)Cl] 4 [HL1 = (2-cyanophenyl)glycine; HL2 = (5-chloro-2-cyanophenyl)glycine; HL3 = (2-cyano-3-fluorophenyl)glycine; HL4 = (4-cyanophenyl)glycine] were synthesized and well characterized by several spectroscopic and analytical techniques. Complexes 1 and 3 were found to be fluorescent in most of the solvents; however, 2 and 4 were found to be fluorescent mostly in EtOAc, DMF and ethanol. Amongst these four complexes, 3 has shown selective sensing against CO 3 2− and SO 4 2− anions by quenching of fluorescence. The LOD values are found to be in the sub-micromolar range. Investigations of the sensing mechanism performed by computation and NMR studies indicate a possible adduct formation between the NH group of the ligand and the anion(s) through hydrogen bond formation, which ultimately might lead to proton transfer to the bi-negative anion. The quantum yield of the complex 3 was found to decrease on addition of CO 3 2− and SO 4 2− anions from 0.46 to 0.13 and 0.12, respectively. The Job's plot indicates the binding between the probe and anion in a 1 : 1 ratio for both CO 3 2− and SO 4 2− anions. Along with that, all the complexes were found to be biocompatible when tested against several cell lines showing very high IC 50 values. It can also be observed that 1 is capable of penetrating within the cells and can act as a cell imaging agent showing fluorescence, and thus can be used for bio-imaging purposes. Four new ruthenium( ii )-arene amino acid complexes were synthesised and characterized by spectrophotometric, analytical and computational techniques. Further evaluation for their sensing, bio-compatibility, and bio-imaging abilities were carried out.