The structure of the lanthanide aquo ions in solution as studied by 17O NMR spectroscopy and DFT calculations

Kristina Djanashvili; Carlos Platas-Iglesias; Joop A. Peters

doi:10.1039/B714801A

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The structure of the lanthanide aquo ions in solution as studied by ¹⁷O NMR spectroscopy and DFT calculations†‡

Kristina Djanashvili,*^a Carlos Platas-Iglesias^b and Joop A. Peters^a

Author affiliations

* Corresponding authors

^a Biocatalysis and Organic Chemistry, Department of Biotechnology, Delft University of Technology, Julianalaan 136, BL Delft, The Netherlands
E-mail: K.Djanashvili@tudelft.nl
Tel: +31 152785092

^b Departamento de Química Fundamental, Universidade da Coruña, Campus da Zapateira, Alejandro de la Sota 1, A Coruña, Spain

Abstract

The ¹⁷O NMR shifts of aqueous samples of lanthanide triflates were measured and analysed. In these systems the triflate anion does not enter the first coordination sphere. The contact contribution to the shifts showed a break at Eu(III), which reflects a change in the number of water molecules in the first coordination sphere of the Ln(III) ion from 9 for La–Sm to 8 for the heavier lanthanides. This change in hydration number is accompanied by a change in the parameters governing the pseudo-contact shifts. Fitting of the data with tricapped trigonal prism and square antiprismatic geometries obtained by DFT (density function theory) calculations showed that the crystal field parameters for these geometries differ by an order of magnitude. The hyperfine coupling constant for both geometries was determined to be A/ℏ = −4.2 × 10⁶ rad s⁻¹.

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Supplementary files

Optimized Cartesian coordinates in aqueous solution for the Ln(H ₂O) ₈ ³⁺ and Ln(H ₂O) ₉ ³⁺ systems (Ln = Ce?Yb, except Pm) and listing of reference codes and literature references of crystal structures of Ln(H ₂O) ₈ ³⁺ ions in a square antiprism coordination polyhedron PDF (153K)

Article information

DOI: https://doi.org/10.1039/B714801A
Article type: Paper
Submitted: 26 Sep 2007
Accepted: 06 Nov 2007
First published: 22 Nov 2007

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Dalton Trans., 2008, 602-607

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The structure of the lanthanide aquo ions in solution as studied by ¹⁷O NMR spectroscopy and DFT calculations

K. Djanashvili, C. Platas-Iglesias and J. A. Peters, Dalton Trans., 2008, 602 DOI: 10.1039/B714801A

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Dalton Transactions