Dataset Information

Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb?DTMA]³⁺ in Aqueous Solution.

ABSTRACT: Yb?DTMA forms a ternary complex with fluoride in aqueous solution by displacement of a bound solvent molecule from the lanthanide ion. [Yb?DTMA?F]²⁺ and [Yb?DTMA?OH₂]³⁺ are in slow exchange on the relevant NMR timescale (<2000?s^-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.

SUBMITTER: Blackburn OA

PROVIDER: S-EPMC4955232 | biostudies-literature | 2015 Sep

REPOSITORIES: biostudies-literature

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Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]3+ in Aqueous Solution.

Blackburn Octavia A OA Chilton Nicholas F NF Keller Katharina K Tait Claudia E CE Myers William K WK McInnes Eric J L EJ Kenwright Alan M AM Beer Paul D PD Timmel Christiane R CR Faulkner Stephen S

Angewandte Chemie (Weinheim an der Bergstrasse, Germany) 20150727 37

Yb⋅DTMA forms a ternary complex with fluoride in aqueous solution by displacement of a bound solvent molecule from the lanthanide ion. [Yb⋅DTMA⋅F]2+ and [Yb⋅DTMA⋅OH2]3+ are in slow exchange on the relevant NMR timescale (<2000 s-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 ...[more]

PMID: 27478267

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Project description:A non-oxido V(v) complex with glutaroimide-dioxime (H3L), a ligand for recovering uranium from seawater, was synthesized from aqueous solution as Na[V(L)2]·2H2O, and the structure determined by X-ray diffraction. It is the first non-oxido V(v) complex that has been directly synthesized in and crystallized from aqueous solution. The distorted octahedral structure contains two fully deprotonated ligands (L3-) coordinating to V5+, each in a tridentate mode via the imide N (RV-N = 1.96 Å) and oxime O atoms (RV-O = 1.87-1.90 Å). Using 17O-labelled vanadate as the starting material, concurrent 17O/51V/1H/13C NMR, in conjunction with ESI-MS, unprecedentedly demonstrated the stepwise displacement of the oxido V 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 O bonds by glutaroimide-dioxime and verified the existence of the "bare" V5+/glutaroimide-dioxime complex, [V(L)2]-, in aqueous solution. In addition, the crystal structure of an intermediate 1?:?1 V(v)/glutaroimide-dioxime complex, [VO2(HL)]-, in which the oxido bonds of vanadate are only partially displaced, corroborates the observations by NMR and ESI-MS. Results from this work provide important insights into the strong sorption of vanadium on poly(amidoxime) sorbents in the recovery of uranium from seawater. Also, because vanadium plays important roles in biological systems, the syntheses of the oxido and non-oxido V5+ complexes and the unprecedented demonstration of the displacement of the oxido VO bonds help with the on-going efforts to develop new vanadium compounds that could be of importance in biological applications.

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Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb?DTMA]³⁺ in Aqueous Solution.

Publications

Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]<sup>3+</sup> in Aqueous Solution.

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Dataset Information

Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb?DTMA]3+ in Aqueous Solution.

Publications

Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]<sup>3+</sup> in Aqueous Solution.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

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Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb?DTMA]³⁺ in Aqueous Solution.