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The development and the photophysical behavior of a transparent ion-exchange membrane based on a pH-sensitive polypyridyl ruthenium(II) complex, [(bpy) 2 Ru II (H 2 bpib)Ru II (bpy) 2 ](ClO 4 ) 4 (bpy = 2,2'-bipyridine, H 2 bpib = 1,4-bis([1,10]phenanthroline[5,6- d ]-imidazol-2-yl)benzene), are experimentally and theoretically reported. The emission spectra of [(bpy) 2 Ru II (H 2 bpib)Ru II (bpy) 2 ]@Nafion film were observed between pH 2 and pH 11 and showed the highest relative emission intensity at pH 5 ( λ  max  em = 594.4 nm). The relative emission intensity of the film significantly decreased down to 75% at pH 2 and 11 compared to that of pH 5. The quantum yields ( Φ ) and lifetimes ( τ ) showed similar correlations with respect to pH, Φ = 0.13 and τ = 1237 ns at pH 5, and Φ = 0.087 and τ = 1014 ns and Φ = 0.069 and τ = 954 ns at pH 2 and pH 11, respectively. These photophysical data are overall considerably superior to those of the solution, with the radiative- ( k  r ) and non-radiative rate constants ( k  nr ) at pH 5 estimated to be k  r = 1.06 × 10 5 s -1 and k  nr = 7.03 × 10 5 s -1 . Density functional theory calculations suggested the contribution of ligand-to-ligand- and intraligand charge transfer to the imidazolium moiety in Ru-H 3 bpib species, implying that the positive charge on the H 3 bpib ligand works as a quencher. The Ru-Hbpib species seems to enhance non-radiative deactivation by reducing the energy of the upper-lying metal-centered excited state. These would be responsible for the pH-dependent " off-on-off " emission behavior.

membranes

Transparent Ion-Exchange Membrane Exhibiting Intense Emission under a Specific pH Condition Based on Polypyridyl Ruthenium(II) Complex with Two Imidazophenanthroline Groups