Ruthenium(II) complexes of 6,7-dicyanodipyridoquinoxaline:  synthesis, luminescence studies, and DNA interaction

Abstract

The hexafluorophosphate and chloride salts of a series of ruthenium(II) complexes incorporating a new dipyridophenazine-based ligand, dicnq (6,7-dicyanodipyrido[2,2-d:2',3'-f]quinoxaline), are synthesized in good-to-moderate yields. These mono ([Ru(phen)₂(dicnq)]²⁺; phen = 1,10 -phenanthroline), bis ([Ru(phen)(dicnq)₂]²⁺), and tris ([Ru(dicnq)₃]²⁺) complexes are fully characterized by elemental analysis, infrared, FAB-MS, H NMR, and cyclic voltammetric methods. Results of absorption titration and thermal denaturation studies reveal that these complexes are moderately strong binders of calf-thymus (CT) DNA, with their binding constants spanning the range (1-3) × 10⁴ M^-1. On the other hand, under the identical set of experimental conditions of light and drug dose, the DNA (pBR 322)-photocleavage abilities of these ruthenium(II) complexes follow the order [Ru(phen)₂(dicnq)]²⁺ > [Ru(phen)(dicnq)₂]²⁺ [Ru(dicnq)₃]²⁺, an order which is the same as that observed for their MLCT emission quantum yields. Steady-state emission studies carried out in nonaqueous solvents and in aqueous media with or without DNA reveal that while [Ru(dicnq)₃]²⁺ is totally nonemissive under these solution conditions, both [Ru(phen)₂(dicnq)]²⁺ and [Ru(phen)(dicnq)₂]²⁺ are luminescent and function as "molecular light switches" for DNA. Successive addition of CT DNA to buffered aqueous solutions containing the latter two complexes results in an enhancement of the emission in each case, with the enhancement factors at saturation being approximately 16 and 8 for [Ru(phen)₂(dicnq)]²⁺ and [Ru(phen)(dicnq)₂]²⁺, respectively. These results are discussed in light of the relationship between the structure-specific deactivations of the MLCT excited states of these metallointercalators and the characteristic features of their DNA interactions, and attempts are made to compare and contrast their properties with those of analogous dipyridophenazine-based complexes, including the ones reported in the preceding paper.