On the determination of the number of water molecules, q, coordinated to europium(III) ions in solution from luminescence decay lifetimes

被引:586
作者
Supkowski, RM
Horrocks, WD
机构
[1] Penn State Univ, Dept Chem, University Pk, PA 16802 USA
[2] WR Grace & Co Conn, Columbia, MD 21044 USA
基金
美国国家科学基金会;
关键词
luminescence; europium complexes; water ligand complexes;
D O I
10.1016/S0020-1693(02)01022-8
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A refined equation (in its simplest form: q = 1.11[tau(H2O)(-1)-tau(D2O)(-1)-0.31]) which allows the prediction of the number of water molecules in the first coordination sphere of a europium(III) (Eu3+) complex, q, in aqueous solution is presented. It is recognized that in the long history of the determination of the q-values of Eu3+ complexes from luminescent data of the excited metal ions in H2O and D2O solutions, certain inconsistencies are present. In some cases the q-values determined have either been non-integral when they should be integral, or have been in conflict with q-values predicted by other means. The original q-value equation put forth by this laboratory correlated the luminescence lifetime data of crystalline Eu3+ complexes to the known q-values based on XRD data from single crystals. In the current report, the difference in the decay rate of the Eu3+ luminescence of metal complexes in H2O and DO solution is linearly correlated to q-values predicted using the original equation as a guide. Our current interpretation of the luminescence data of 25 Eu3+ complexes taken from the literature, along with the extensive research of many labs involving the effect of oscillators other than water molecules in the first coordination sphere of the Eu3+ ion, has yielded the following equation: q = 1.11[tau(H2O)(-1)-tau(D2O)(-1)-0.31+0.45n(OH)+0.99n(NH)+0.075n(O=CNH)] where n(OH) is the number of alcoholic O-H oscillators in the first coordination sphere of Eu3+, and n(O=CNH) is the number of amide N-H oscillators in the first coordination sphere of Eu3+ n(NH) is the number of amine oscillators in which the amide carboxylic oxygen is in the first coordination sphere of Eu3+. The coefficient of determination parameter of the linear least-squares fit to the data is 0.998 and the standard error of the tit is +/-0.1 in q. The equation is used to account for the effect of water molecules in the second coordination sphere of the Eu3+ ion as well as to cast light on aqueous Eu3+ complexes that have known labile coordination spheres. (C) 2002 Elsevier Science B.V. All rights reserved.
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页码:44 / 48
页数:5
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