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Are luminescent Ru 2+ chelated complexes selective coordinative sensors for the detection of heavy cations?
- Source :
-
Physical chemistry chemical physics : PCCP [Phys Chem Chem Phys] 2022 Jan 26; Vol. 24 (4), pp. 2309-2317. Date of Electronic Publication: 2022 Jan 26. - Publication Year :
- 2022
-
Abstract
- The ability of [Ru(bpy) <subscript>2</subscript> (bpym)] <superscript>2+</superscript> (bpy = 2,2'-bipyridine; bpym = 2,2'-bipyrimidine) to probe specifically heavy cations has been investigated by means of density functional theory for transition metals, group 12 elements and Pb <superscript>2+</superscript> . On the basis of the calculated Gibbs free energies of complexation in water it is shown that all reactions are favorable with negative enthalpies except for Hg <superscript>2+</superscript> , with the transition metal cations forming stable bi-metallic complexes by coordination to the bpym ligand. Comparison between the optical and photophysical properties of the Ru <superscript>2+</superscript> probe and those of the coordination compounds does not demonstrate a high selectivity due to very similar characteristics of the absorption and emission spectra. Whereas by complexation the lowest metal-to-ligand-charge-transfer (MLCT) shoulder of [Ru(bpy) <subscript>2</subscript> (bpym)] <superscript>2+</superscript> at 462 nm is more or less shifted to the red as a function of the cation, the second MLCT band at 415 nm, less sensitive to the complexation, gains in intensity and is slightly blue-shifted. The visible MLCT emission of [Ru(bpy) <subscript>2</subscript> (bpym)] <superscript>2+</superscript> at 706 nm is altered by complexation leading to near IR (800-900 nm) emission in most of the coordination compounds. Complexation to some transition metal cations (Fe, Co, Rh and Pd) generates low-lying metal-centered (MC) excited states that quench luminescence. In contrast to the conclusion of experimental findings by Kumar et al. ( Chem. Commun. 2014, 50 , 8488-8490), [Ru(bpy) <subscript>2</subscript> (bpym)] <superscript>2+</superscript> cannot be proposed as a fast and selective probe for monitoring Pd <superscript>2+</superscript> in aqueous media. Indeed, it does not possess the optical and photophysical characteristics necessary to discriminate Pd <superscript>2+</superscript> ions over a variety of other cations.
Details
- Language :
- English
- ISSN :
- 1463-9084
- Volume :
- 24
- Issue :
- 4
- Database :
- MEDLINE
- Journal :
- Physical chemistry chemical physics : PCCP
- Publication Type :
- Academic Journal
- Accession number :
- 35015003
- Full Text :
- https://doi.org/10.1039/d1cp04442g