Spectroscopic and Crystal Field Consequences of Fluoride Binding by [YbDTMA]3+ in Aqueous Solution

被引：50

作者：

Blackburn, Octavia A. ^{[1
]}

Chilton, Nicholas F. ^{[2
,3
]}

Keller, Katharina ^{[4
]}

Tait, Claudia E. ^{[4
]}

Myers, William K. ^{[4
]}

McInnes, Eric J. L. ^{[2
,3
]}

Kenwright, Alan M. ^{[5
]}

Beer, Paul D. ^{[1
]}

Timmel, Christiane R. ^{[4
]}

Faulkner, Stephen ^{[1
]}

机构：

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

[2] Univ Manchester, Sch Chem, Manchester M13 9PL, Lancs, England

[3] Univ Manchester, Photon Sci Inst, Manchester M13 9PL, Lancs, England

[4] Univ Oxford, Ctr Adv ESR CAESR, Inorgan Chem Lab, Oxford OX1 3QR, England

[5] Univ Durham, Dept Chem, Durham DH1 3LE, England

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2015年 / 54卷 / 37期

基金：

英国工程与自然科学研究理事会; 欧洲研究理事会;

关键词：

anion coordination; lanthanide; magnetic anisotropy; NMR spectroscopy; spectroscopic methods; MAGNETIC-RESONANCE SHIFTS; LANTHANIDE COMPLEXES; ANISOTROPY; EXCHANGE; DYNAMICS; IONS; NMR;

D O I：

10.1002/anie.201503421

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

YbDTMA forms a ternary complex with fluoride in aqueous solution by displacement of a bound solvent molecule from the lanthanide ion. [YbDTMAF](2+) and [YbDTMAOH(2)](3+) are in slow exchange on the relevant NMR timescale (<2000s(-1)), and profound differences are observed in their respective NMR and EPR spectra of these species. The observed differences can be explained by drastic modification of the ligand field states due to the fluoride binding. This changes the magnetic anisotropy of the Yb-III ground state from easy-axis to easy-plane type, and this change is easily detected in the observed magnetic anisotropy despite thermal population of more than just the ground state. The spectroscopic consequences of such drastic changes to the ligand field represent important new opportunities in developing fluoride-responsive complexes and contrast agents.

引用

页码：10783 / 10786

页数：4

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