Ruthenium(II) and Osmium(II) Mixed Chelates Based on Pyrenyl–Pyridylimidazole and 2,2′-Bipyridine Ligands as Efficient DNA Intercalators and Anion Sensors
2015-01-20T00:00:00Z (GMT) by
We report herein the synthesis and characterization of two monometallic ruthenium(II) and osmium(II) complexes of composition [(bpy)2M(HImzPPy)] (ClO4)2 derived from pyrenylimidazole–10-pyridin-2-yl-9H-9,11-diazacyclopenta[e]pyrene (HImzPPy) and 2,2′-bipyridine (bpy) ligands. X-ray crystallographic study shows that both crystals belong to the triclinic system having space group P1̅. The photophysical properties of 1 and 2 in acetonitrile indicate that the metal-to-ligand charge-transfer excited state is mainly centered in the [M(bpy)2]2+ moiety of the complexes and slightly affected by the extended conjugation of the pyrenylimidazole moiety. Both complexes display one-electron reversible metal-centered oxidative processes and a number of quasi-reversible reductive processes. The binding affinities of the complexes toward calf-thymus DNA (CT-DNA) were thoroughly studied through different methods such as absorption, emission, excited-state lifetime, circular dichroism, and thermal denaturation of DNA and a relative DNA binding study using ethidium bromide. All of these experiments account for the intercalative nature of both 1 and 2 toward CT-DNA as well as their light-switch behavior. The anion recognition study through different spectroscopic techniques reveals that both complexes act as “turn-on” luminescence sensors for H2PO4− and “turn-off” sensors toward F– and AcO–. The imidazole N–H proton of the receptors gets deprotonated with the excessive addition of F– and AcO–, while it interacts with H2PO4– through hydrogen-bonding interaction. Theoretical calculations (DFT and TD-DFT) were also performed to understand the photophysical properties of the metalloreceptors.