Formation kinetics of europium(III) complexes of DOTA and its bis(phosphonate) bearing anlogs

被引：10
作者：
Prochazkova, Sona [1 ]
Hranicek, Jakub [2 ]
Kubicek, Vojtech [1 ]
Hermann, Petr [1 ]
机构：
[1] Charles Univ Prague, Dept Inorgan Chem, Fac Sci, Hlavova 2030, CR-12840 Prague 2, Czech Republic
[2] Charles Univ Prague, Dept Analyt Chem, Fac Sci, Hlavova 2030, CR-12840 Prague 2, Czech Republic
来源：
POLYHEDRON | 2016年 / 111卷
关键词：
Dota-like ligands; Complexation mechanism; Kinetics; Lanthanide(III) complexes; Bisphosphonate; LANTHANIDE(III) COMPLEXES; DISSOCIATION KINETICS; EU(III) COMPLEXES; LIGAND; LUMINESCENCE; INTERMEDIATE; SPECTROSCOPY; EQUILIBRIUM; RADIOMETALS; DERIVATIVES;
D O I：
10.1016/j.poly.2016.03.039
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
Complexation of Eu(III) ions with H(4)dota and its bis(phosphonate)-bearing analogs, H(8)do3aP(BP) with phosphinate spacer and H(7)dotam(BP) with carboxamide spacer, was studied by UV-Vis spectrophotometry and luminescence life-time measurements. The results show formation of two types of out-of-cage intermediates. The [EuL](oc) intermediate is formed under metal ion excess, whereas [EuL2](oc) intermediate is formed under ligand excess. At room temperature, their conversion to in-cage complex is comparable but the [EuL2](oc) transformation into the in-cage complex is significantly faster at elevated temperatures. Both bis(phosphonate)-bearing ligands show slower complexation rate than H(4)dota. Comparison of reactivity of H(8)do3aP(BP) and H(7)dotam(BP) show important role of the spacer connecting the bis(phosphonate) group with the macrocycle. Presence of phosphinate in H(8)do3aP(BP) leads to significantly faster (3-4 orders of magnitude) complexation than in case of the amide spacer in H(7)dotam(BP). Both bis(phosphonate)-bearing ligands show nonlinear dependence of the complexation rate on concentration of hydroxide anions due to changes in protonation state of the bis(phosphonate) moiety. (C) 2016 Elsevier Ltd. All rights reserved.
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页码：143 / 149
页数：7
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