Off-on-off pH luminescence switching and DNA binding properties of a free terpyridine-appended ruthenium complex

A ruthenium(II) complex [Ru(bpy)(2)(HL1)](ClO4)(2)center dot 3H(2)O {bpy = 2,2'-bipyridine and HL1 = 2-(2,6-di(pyridin-2-yl)pyridin-4-yl)-1H-imidazo[4,5-f][1,10]phenanthroline}, denoted as RuHL1, was synthesized and characterized by elemental analysis, proton nuclear magnetic resonance spectroscopy, and mass spectrometry. The pH effects on the UV-visible (UV-vis) absorption and emission spectra and the luminescence lifetimes of RuHL1 have been studied, and their ground- and excited-state acid ionization constants were derived. The complex was found to exhibit pH-induced "off-on-off" luminescence switching properties via protonation/deprotonation of the grafted imidazole and terpyridyl groups. A pH-induced emission on-off intensity ratio of 166 was observed as pH was increased from 2.00 to 5.44, which is one of the largest values observed among imidazole-containing Ru(II) complex-based acidic-pH-induced pH luminescence switches. RuHL1 also strongly binds to calf thymus DNA in mixed binding modes involving classic intercalation and partial intercalation, as determined by UV-vis absorption and emission spectrophotometric DNA titration, ethidium bromide displacement, DNA denaturation and DNA viscosity measurements. (C) 2014 Elsevier Inc. All rights reserved.