Braun, D. and Huber, P. and Wudy, J. and Schmidt, J. and Yersin, Hartmut (1994) Electron delocalization and localization in mixed-ligand [Ru(LL)n(LL')3-n]²⁺ complexes. The Journal of Physical Chemistry 98 (33), pp. 8044-8049.
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Highly resolved emission spectra of isolated [Ru(LL)n(LL')3-nJ²⁺ complexes doped into [Zn(bpy)₃](ClO₄)₂ with LL and LL' representing the ligands bpy-h₈, bpy-d₈, 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)₂(bpz)]²⁺ only the ligand-centered modes of bpz can be found in the emission spectra. In contrast, for [Ru(bpy-h₈)₂(bpy-d₈)]²⁺ the ligand-centered vibrations of bpy-h₈ and bpy-d₈ accompany the same electronic origin. This is strong evidence for the delocalization of the excited electron in mixed-ligand [Ru(bpy-h₈)₂(bpy-d₈)]²⁺. Consequently, the lowest MLCT excited states in homoleptic complexes like [Ru(bpy-h₈)₃]²⁺ and [Ru(bpy-d₈)₃]²⁺ are also delocalized over the metal and the different ligands.
|Institutions:||Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry III - Physical Chemistry (Light and Matter) > Prof. Dr. Hartmut Yersin|
|Subjects:||500 Science > 540 Chemistry & allied sciences|
|Refereed:||Yes, this version has been refereed|
|Created at the University of Regensburg:||Yes|
|Owner:||Prof. Dr. Hartmut Yersin|
|Deposited On:||01 Mar 2011 12:28|
|Last Modified:||01 Mar 2011 12:28|
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