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Non-radiative deactivation of the excited states of europium, terbium and ytterbium complexes by proximate energy-matched OH, NH and CH oscillators: an improved luminescence method for establishing solution hydration states

Abstract:
The radiative rate constants for depopulation of the excited states of closely-related series of anionic, neutral and cationic europium, terbium and ytterbium complexes have been measured in H2O and D2O. With the aid of selective liuand deuteriation, the relative contributions of OH, NH (both amide and amine) and CH oscillators have been measured and critically assessed. Quenching of the Eu 5D0 excited state by amine NH oscillators is more than twice as efficient as OH quenching. The importance of the distance between the excited Ln ion and the XH oscillator is described with recourse to published crystallographic information. The general equation, q = A′(ΔkH2O-kD2O)corr is presented and revised values of A′ for Eu (1.2 ms), Tb (5 ms) and Yb(1 μs) given, which allow for the quenching contribution of closely diffusing OH oscillators. The relevance of such studies to the hydration state of certain gadolinium complexes is described and clear evidence provided for a break in hydration at gadolinium.
Publication status:
Published

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Publisher copy:
10.1039/a808692c

Authors

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Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Inorganic Chemistry
Role:
Author


Journal:
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 More from this journal
Issue:
3
Pages:
493-503
Publication date:
1999-03-01
DOI:
EISSN:
1364-5471
ISSN:
1472-779X


Language:
English
Pubs id:
pubs:46811
UUID:
uuid:6c634d6e-2bf9-4c7d-b160-09d6fefcfc10
Local pid:
pubs:46811
Source identifiers:
46811
Deposit date:
2012-12-19
ARK identifier:

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