Exploitation of the Second Coordination Sphere to Promote Significant Increase of Room-Temperature Luminescence Lifetime and Anion Sensing in Ruthenium–Terpyridine Complexes

Abstract

This paper deals with the synthesis, characterization, and photophysical behaviors of three Ru(II)-terpyridine complexes derived from a terpyridyl-imidazole ligand (tpy-HImzPh3Me2), wherein a terpyridine moiety has been coupled with a dimethylbenzil unit through a phenylimidazole spacer. The three complexes display strong emission at RT having excited-state lifetimes in the range of 2.3-43.7 ns, depending upon the co-ligand present and the solvents used. Temperature-dependent emission spectral measurements have demonstrated that the energy separation between emitting metal-to-ligand charge transfer state and non-emitting metal-centered state is increased relative to that of [Ru(tpy)2]2+. In contrast to our previously studied Ru(II) complexes containing similar terpyridyl-imidazole motif but differing by peripheral methyl groups, significant enhancement of RT emission intensity and quantum yield and remarkable increase of emission lifetime occur for the present complexes upon protonation of the imidazole nitrogen(s) with perchloric acid. Additionally, by exploiting imidazole NH motif(s), we have examined their anion recognition behaviors in organic and aqueous media. Interestingly, the complexes are capable of visually recognizing cyanide ions in aqueous medium up to the concentration limit of 10-8 M. Computational studies involving density functional theory (DFT) and time-dependent DFT methods have been carried out to obtain insights into their electronic structures and to help with the assignment of absorption and emission bands.