Electron delocalization and localization in mixed-ligand [Ru(LL)[sub n](LL[prime])[sub 3[minus]n]][sup 2+] complexes

Journal Article · Thu Aug 18 00:00:00 EDT 1994 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100084a021· OSTI ID:6994469

Braun, D; Huber, P; Wudy, J; Schmidt, J; Yersin, H ^[1]

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1. Universitaet Regensburg (Germany)

Highly resolved emission spectra of isolated [Ru(LL)[sub n](LL[prime])[sub 3[minus]n]][sup 2+] complexes doped into [Zn(bpy)[sub 3]] (ClO[sub 4])[sub 2] with LL and LL[prime] representing the ligands bpy-h[sub g], bpy-d[sub g], and bpz are presented. The information displayed in the electronic origins and the vibrational satellite structures combined with the emission decay behavior is used to provide a clear distinction between localized and delocalized MLCT transitions to the lowest excited states. In particular, the appearance or nonappearance of ligand-centered vibrational modes belonging to different types of ligands provides crucial evidence for delocalization or localization. Thus, for a localized excitation in [Ru(bpy)[sub 2](bpz)][sup 2+] only the ligand-centered modes of bpz can be found in the emission spectra. In contrast, for [Ru(bpy-h[sub g])[sub 2](bpy-d[sub g])][sup 2+] the ligand-centered vibrations of bpy-h[sub g] and bpy-d[sub g] accompany the same electronic origin. This is strong evidence for the delocalization of the excited electron in mixed-ligand [Ru(bpy-h[sub g])[sub 2](bpy-d[sub g])][sup 2+]. Consequently, the lowest MLCT excited states in homoleptic complexes like [Ru(bpy-h[sub g])[sub 3]][sup 2+] and [Ru(bpy-d[sub g])[sub 3]][sup 2+] are also delocalized over the metal and the different ligands. 39 refs., 4 figs., 1 tab.

• OSTI ID: 6994469
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 98:33; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

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ACETONE
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL DOPING
EMISSION SPECTRA
ENERGY LEVELS
EXCITED STATES
KETONES
LASERS
LIGANDS
LUMINESCENCE
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOSYNTHESIS
RUTHENIUM COMPLEXES
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
VIBRATIONAL STATES
ZINC COMPLEXES