Issue 10, 2010
From the journal:

CrystEngComm

Solid-state 51V MAS NMR spectroscopy determines component concentration and crystal phase in co-crystallised mixtures of vanadium complexes†

Ulla Gro Nielsen,a   Alan Hazell,b   Jørgen Skibsted,b   Hans J. Jakobsenb  and  Christine J. McKenzie*a  

* Corresponding authors

a University of Southern Denmark, Department of Physics and Chemistry, Campusvej 55, Odense M, Denmark
E-mail: ugn@ifk.sdu.dk, chk@ifk.sdu.dk
Fax: +45 6615 8780
Tel: +45 6550 2518

b Aarhus University, Department Chemistry, Langelandsgade 140, Aarhus C, Denmark
E-mail: ach@chem.au.dk, jskib@chem.au.dk, hja@chem.au.dk

Abstract

The oxo-peroxo-vanadium(V) and dioxo-vanadium(V) complexes of N,N-bis(2-pyridylmethyl)glycinate (bpg−), VO(O2)(bpg) (1) and V(O)2(bpg) (2) co-crystallize in variable ratios in an anhydrous and a dihydrate phase with the overall formulation 1x21−x·nH2O, n = 0 or 2, where 0 ≤ x ≤ 1 (alternatively V(O)2−x(O2)x(bpg)·nH2O, n = 0 or 2, where 0 ≤ x ≤ 1). The seven-coordinated complex 1 contains a η2-peroxide ligand (O22−) whereas the six coordinated 2 contains a monoatomic oxide ligand (O2−) in the same position. Characteristic chemical shift differences for the vanadium atoms of the two complexes mean that 51V solution state and MAS NMR spectroscopy can be used to determine the concentration of 1 and 2 in bulk samples. Significantly, however, 51V MAS NMR spectroscopy also reports on the identity of the crystal phase. This is possible because the isotropic 51V resonances are sensitive to intermolecular interactions specific to each crystal phase. The solid-state 51V MAS NMR spectroscopic data show that the different phases do not co-precipitate but the concentration of the solute (which can be either 1 or 2) can vary. Thus co-crystallised mixtures of 1 and 2 can be classed as a molecular mixture capable of forming continuous solid solutions.

Graphical abstract: Solid-state 51V MAS NMR spectroscopy determines component concentration and crystal phase in co-crystallised mixtures of vanadium complexes

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Article information

DOI
https://doi.org/10.1039/B922687G
Article type
Paper
Submitted
29 Oct 2009
Accepted
29 Mar 2010
First published
30 Apr 2010

CrystEngComm, 2010,12, 2826-2834

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Solid-state 51V MAS NMR spectroscopy determines component concentration and crystal phase in co-crystallised mixtures of vanadium complexes

U. G. Nielsen, A. Hazell, J. Skibsted, H. J. Jakobsen and C. J. McKenzie, CrystEngComm, 2010, 12, 2826 DOI: 10.1039/B922687G

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