| Item type: | Article |
|---|---|
| Journal or Publication Title: | Coordination Chemistry Reviews |
| Publisher: | Elsevier |
| Volume: | 208 |
| Page Range: | pp. 75-93 |
| Date: | 2002 |
| Institutions: | Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry III - Physical Chemistry (Molecular Spectroscopy and Photochemistry) > Prof. Dr. Hartmut Yersin |
| Dewey Decimal Classification: | 500 Science > 540 Chemistry & allied sciences |
| Status: | Published |
| Refereed: | Yes, this version has been refereed |
| Created at the University of Regensburg: | Yes |
| Item ID: | 17477 |
Abstract
{Λ-[Ru(bpy)₃] Δ-[Os(bpy)₃]}(PF₆)₄ is the first representative of a new class of materials. The crystal structure is built up of homochiral layers of Λ-[Ru(bpy)₃]²⁺ that alternate with homochiral layers of Δ-[Os(bpy)₃]²⁺. In this new material, the excitation energy is transferred efficiently by radiationless processes to one single crystallographic site of Δ-[Os(bpy)₃]²⁺ (site A), where the ...
Abstract
{Λ-[Ru(bpy)₃] Δ-[Os(bpy)₃]}(PF₆)₄ is the first representative of a new class of materials. The crystal structure is built up of homochiral layers of Λ-[Ru(bpy)₃]²⁺ that alternate with homochiral layers of Δ-[Os(bpy)₃]²⁺. In this new material, the excitation energy is transferred efficiently by radiationless processes to one single crystallographic site of Δ-[Os(bpy)₃]²⁺ (site A), where the excitation energy is harvested. We develop an understanding of: (1) the different steps of energy transfer, (2) the dominating mechanisms (Förster and/or Dexter), and (3) the electronic states involved. Therefore, we study, typically at T=1.3 K, properties of the low-lying excited states and of energy transfer processes occurring in rac-[Ru(bpy)₃](PF₆)₂, [Ru1-xOsx(bpy)₃](PF₆)₂ (with x=0.01, 0.1, 0.2, and 1.0) and we compare the results to those obtained for {Λ-[Ru(bpy)₃] Δ-[Os(bpy)₃]}(PF₆)₄. It can be concluded for this latter compound that the different inter-layer and intra-layer steps of energy transfer to the lowest site of Δ-[Os(bpy)₃]²⁺ are dominated by efficient Dexter exchange processes. Due to energy accumulation at this lowest site, the new compound exhibits the interesting property of self-site-selectivity. This means, one obtains one-site emission spectra for every excitation wavelength from the UV to 693 nm. And since this lowest site of Δ-[Os(bpy)₃]²⁺ is well shielded from its environment, the spectra are highly resolved and thus reveal directly detailed properties of the low-lying electronic states and their vibronic coupling behavior. In particular, these properties depend strongly on an applied magnetic field. For example, with application of a field up to H=12 T, the intensity of the lowest electronic 0-0 transition can be tuned in and increased by several orders of magnitude. Simultaneously, the vibrational satellite structure is completely altered. We observe changes from a vibronically induced (Herzberg-Teller) structure to a structure dominated by Franck-Condon satellites. This property of Δ-[Os(bpy)₃]²⁺ is due to a magnetically induced coupling between lower lying triplet substates. Similar observations have not yet been reported for other compounds.
Metadata last modified: 24 May 2018 12:17
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