Substituent effects on fluoride binding by lanthanide complexes of DOTA-tetraamides

被引：28

作者：

Blackburn, Octavia A. ^{[1
]}

Routledge, Jack D. ^{[1
]}

Jennings, Laura B. ^{[1
]}

Rees, Nicholas H. ^{[1
]}

Kenwright, Alan M. ^{[2
]}

Beer, Paul D. ^{[1
]}

Faulkner, Stephen ^{[1
]}

机构：

[1] Univ Oxford, Chem Res Lab, 12 Mansfield Rd, Oxford OX1 3TA, England

[2] Univ Durham, Dept Chem, South Rd, Durham DH1 3LE, England

来源：

DALTON TRANSACTIONS | 2016年 / 45卷 / 07期

基金：

欧洲研究理事会;

关键词：

HYDRATION; EXCHANGE; LUMINESCENCE; ANISOTROPY; TERBIUM; SHIFTS; RATES; NMR;

D O I：

10.1039/c5dt04349b

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Fluoride binding by a series of europium and ytterbium complexes of DOTA-tetraamide ligands derived from primary, secondary and tertiary amides has been studied by NMR and luminescence spectroscopies. In all the systems studied, fluoride binding results in a change in the nature of the magnetic anisotropy at the metal centre from an easy axis, to an easy plane anisotropy. This results in reversal of the peaks in the NMR spectra, and in changes to the fine structure of the luminescence spectra. Furthermore, changes to the periphery of the binding cavity are implicated in determining the affinity constant for fluoride. There are clear differences in the entropic contribution to the free energy of activation between systems with benzylic amides and those with methylamides.

引用

页码：3070 / 3077

页数：8

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