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

In this work, four new ruthenium complexes [Ru(η6-p-cymene)(L1)Cl] 1, [Ru(η⁶-p-cymene)(L2)Cl] 2, [Ru(η⁶-p-cymene)(L3)Cl] 3 and [Ru(η⁶-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 CO₃²⁻ and SO₄²⁻ 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 CO₃²⁻ and SO₄²⁻ 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 CO₃²⁻ and SO₄²⁻ anions. Along with that, all the complexes were found to be biocompatible when tested against several cell lines showing very high IC₅₀ 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.