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Intramolecular deactivation processes of electronically excited Lanthanide(III) complexes with organic acids of low molecular weight

  • The luminescence of Lanthanide(Ill) complexes with different model ligands was studied under direct as well as sensitized excitation conditions. The research was performed in the context of studies dealing with deep-underground storages for high-level nuclear waste. Here, Lanthanide(III) ions served as natural analogues for Actinide(III) ions and the low-molecular weight organic ligands are present in clay minerals and furthermore, they were employed as proxies for building blocks of humic substances, which are important complexing molecules in the natural environment, e.g., in the far field of a repository site. Time-resolved luminescence spectroscopy was applied for a detailed characterization of Eu(III), Tb(III), Sm(III) and.Dy(III) complexes in aqueous solutions. Based on the observed luminescence the ligands were tentatively divided into two groups (A, B). The luminescence of Lanthanide(III) complexes of group A was mainly influenced by an energy transfer to OH-vibrations. Lanthanide(Ill) complexes of group B showedThe luminescence of Lanthanide(Ill) complexes with different model ligands was studied under direct as well as sensitized excitation conditions. The research was performed in the context of studies dealing with deep-underground storages for high-level nuclear waste. Here, Lanthanide(III) ions served as natural analogues for Actinide(III) ions and the low-molecular weight organic ligands are present in clay minerals and furthermore, they were employed as proxies for building blocks of humic substances, which are important complexing molecules in the natural environment, e.g., in the far field of a repository site. Time-resolved luminescence spectroscopy was applied for a detailed characterization of Eu(III), Tb(III), Sm(III) and.Dy(III) complexes in aqueous solutions. Based on the observed luminescence the ligands were tentatively divided into two groups (A, B). The luminescence of Lanthanide(III) complexes of group A was mainly influenced by an energy transfer to OH-vibrations. Lanthanide(Ill) complexes of group B showed ligand-related luminescence quenching, which was further investigated. To gain more information on the underlying quenching processes of group A and B ligands, measurements at different temperatures (77 K <= T <= 353 K) were performed and activation energies were determined based on an Arrhenius analysis. Moreover, the influence of the ionic strength between 0 M <= 1 <= 4 M on the Lanthanide(III) luminescence was monitored for different complexes, in order to evaluate the influence of specific conditions encountered in host rocks foreseen as potential repository sites.show moreshow less

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Metadaten
Author details:Katja Burek, Sascha EidnerORCiD, Stefanie Kuke, Michael Uwe KumkeORCiDGND
DOI:https://doi.org/10.1016/j.saa.2017.09.012
ISSN:1386-1425
Pubmed ID:https://pubmed.ncbi.nlm.nih.gov/28982067
Title of parent work (English):Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
Publisher:Elsevier
Place of publishing:Oxford
Publication type:Article
Language:English
Date of first publication:2018/09/17
Publication year:2018
Release date:2022/01/24
Tag:Benzoic acids; Humic substance; Intramolecular deactivation; Metal complexation; Model ligand
Volume:191
Number of pages:14
First page:36
Last Page:49
Funding institution:Federal Ministry of Economic Affairs and Energy (BMWi)Federal Ministry for Economic Affairs and Energy (BMWi) [02E11011]
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Physik und Astronomie
DDC classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Peer review:Referiert
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