Two star-shaped tetranuclear Ru(II) complexes containing uncoordinated imidazole groups: synthesis, characterization, photophysical and pH sensing properties.

Abstract

Tetrapodal ligands H4L(1) and H4L(2) containing imidazole groups have been synthesized by the reaction of 1,10-phenanthroline-5,6-dione with 1,2,4,5-tetrakis[(4-formylphenoxy)methyl]benzene and 1,2,4,5-tetrakis[(3-formylphenoxy)methyl]benzene, respectively, in presence of NH4OAc. Two star-shaped complexes [{Ru(bpy)2}4(μ4-H4L(1))](PF6)8 and [{Ru(bpy)2}4(μ4-H4L(2))](PF6)8 (bpy = 2,2'-bipyridine) have been prepared by refluxing Ru(bpy)2Cl2 ·2H2O and each ligand in ethylene glycol. The deprotonated complexes [{Ru(bpy)2}4(μ4-L(1))](PF6)4 and [{Ru(bpy)2}4(μ4-L(2))](PF6)4 have been obtained by the reaction of sodium methoxide with [{Ru(bpy)2}4(μ4-H4L(1))](PF6)8 and [{Ru(bpy)2}4(μ4-H4L(2))](PF6)8, respectively, in methanol. The pH effects on the UV-vis light absorption and emission spectra of both complexes have been studied, and ground- and excited-state ionization constants of both complexes have been derived. The photophysical properties of both complexes are strongly dependent on the solution pH. They act as proton-induced off-on-off luminescent sensors through two successive deprotonation processes of imidazole groups, with a maximum on-off ratio of 8 in buffer solution at room temperature. Theoretical calculations for the highest occupied molecular orbital (HOMO) and lowest occupied molecular orbital (LOMO) orbitals of bridging ligand are also presented for plausible explanations of the fluorescence changes.