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The nephelauxetic effect of Eu(III)-N-donor compounds probed using fluorescence spectroscopy: further evidence for covalence?

The 7F0 emission bands of Eu(III)-N-donor complexes are investigated using time resolved laser fluorescence spectroscopy (TRLFS) and fluorimetry. The observed bathochromic shifts resulting from the complexation of Eu(III) with N-donor ligands are considerably more pronounced than those observed for...

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Bibliographic Details
Main Authors: Wagner, Christoph (Author) , Ruff, Christian (Author) , Müllich, Udo (Author) , Geist, Andreas (Author) , Panak, Petra (Author)
Format: Article (Journal)
Language:English
Published: [2016]
In: New journal of chemistry
Year: 2016, Volume: 40, Issue: 11, Pages: 9232-9237
ISSN:1369-9261
DOI:10.1039/C6NJ01705C
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1039/C6NJ01705C
Verlag, lizenzpflichtig, Volltext: https://pubs.rsc.org/en/content/articlelanding/2016/nj/c6nj01705c
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Author Notes:Christoph Wagner, Christian Ruff, Udo Müllich, Andreas Geist and Petra J. Panak
Description
Summary:The 7F0 emission bands of Eu(III)-N-donor complexes are investigated using time resolved laser fluorescence spectroscopy (TRLFS) and fluorimetry. The observed bathochromic shifts resulting from the complexation of Eu(III) with N-donor ligands are considerably more pronounced than those observed for hard oxygen donor ligands. The magnitude of these shifts results from a strong nephelauxetic effect caused by the interaction of Eu(III) with N-donor ligands. Since the extent of the nephelauxetic effect is correlated with the degree of covalence in a metal-ligand bond, the results prove a significant share of covalence in the Eu(III)-N-donor bonds in addition to electrostatic interactions. Furthermore, a linear correlation between the shift of the 7F0 emission band of the Eu(III) complexes with BT(B)P/BTPhen ligands relative to the Eu(III) aquo ion and the number of N-donors in the first coordination sphere of Eu(III) is established: CNL = 0.109·Δν + 0.134, [Δν] = cm−1. Taking into account the known denticity of BTP/BTBP/BTPhen ligands the stoichiometry of the investigated complexes is easily determined by using the above equation.
Item Description:Gesehen am 05.06.2020
Physical Description:Online Resource
ISSN:1369-9261
DOI:10.1039/C6NJ01705C

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