title: Steady-state and time-resolved luminescence of Ru(II) polypyridine complexes attached to Ag nanoparticles: Effect of chemisorption in comparison with electrostatic bonding.
abstract: Steady state and nanosecond time resolved luminescence (namely, (3)MLCT phosphorescence) of [Ru(bpy)3](2+) and of [Ru(bpy)2(dcbpy)](2+)/bpy=2,2'-bipyridine; dcbpy=2,2'-bipyridyl-4,4'-dicarboxylic acid/attached to Ag NPs (the former by the electrostatic bonding, the latter by chemisorption) in non-aggregated Ag NP hydrosol systems has been investigated, and compared to the luminescence characteristics of the complexes in aqueous solutions. The intensity decrease of the 452 nm (and/or 455 nm, respectively) main band and elimination of the short wavelength shoulders in the excitation spectra and the intensity decrease of the emission spectra observed for both complexes upon their attachment to Ag NPs is attributed to the overlap of the excitation spectra with the surface plasmon extinction (SPE) of Ag NPs. The overlap leads to a loss of excitation energy by SPE as well as to a decrease of the (1)MLCT to (3)MLCT intersystem crossing efficiency. The time-resolved luminescence study shows that the (3)MLCT phosphorescence lifetimes of both complexes are markedly (by 3 and 4 orders of magnitude, respectively) shortened upon their attachment to Ag NPs. Nevertheless, the (3)MLCT lifetime of the chemisorbed [Ru(bpy)2(dcbpy)](2+) is by at least one order of magnitude shorter than that of the electrostatically bonded [Ru(bpy)3](2+), which indicates, that the phosphorescence lifetimes of these luminophores are strongly affected by the type of Ag NP surface-luminophore bonding.
authors.affiliation: Department of Physical and Macromolecular Chemistry, Charles University in Prague, Hlavova 8, Prague 2, 128 40, Czech Republic. Electronic address: marketa.kokoskova@natur.cuni.cz.
authors.forename: Markéta
authors.initials: M
authors.lastname: Kokošková
authors.affiliation: Department of Physical and Macromolecular Chemistry, Charles University in Prague, Hlavova 8, Prague 2, 128 40, Czech Republic.
authors.forename: Miroslav
authors.initials: M
authors.lastname: Štěpánek
authors.affiliation: Department of Physical and Macromolecular Chemistry, Charles University in Prague, Hlavova 8, Prague 2, 128 40, Czech Republic.
authors.forename: Ivana
authors.initials: I
authors.lastname: Šloufová
authors.affiliation: Department of Physical and Macromolecular Chemistry, Charles University in Prague, Hlavova 8, Prague 2, 128 40, Czech Republic. Electronic address: vlc@natur.cuni.cz.
authors.forename: Blanka
authors.initials: B
authors.lastname: Vlčková
keywords: Ag nanoparticles; Luminescence; Ru(II) bis(2,2-bipyridine)(2,2′-bipyridyl-4,4′-dicarboxylic acid); Ru(II) tris(2,2-bipyridine); Surface–luminophore bonding