title: NMR crystallography of an oxovanadium(V) complex by an approach combining multinuclear magic angle spinning NMR, DFT, and spin dynamics simulations.
abstract: Bioinorganic vanadium(V) solids are often challenging for structural analysis. Here, we explore an NMR crystallography approach involving multinuclear (13) C/(51) V solid-state NMR spectroscopy, density functional theory (DFT), and spin dynamics numerical simulations, for the spectral assignment and the 3D structural analysis of an isotopically unmodified oxovanadium(V) complex, containing 17 crystallographically inequivalent (13) C sites. In particular, we report the first NMR determination of C-V distances. So far, the NMR observation of (13) C-(51) V proximities has been precluded by the specification of commercial NMR probes, which cannot be tuned simultaneously to the close Larmor frequencies of these isotopes (100.6 and 105.2 MHz for (13) C and (51) V, respectively, at 9.4 T). By combining DFT calculations and (13) C-(51) V NMR experiments, we propose a complete assignment of the (13) C spectrum of this oxovanadium(V) complex. Furthermore, we show how (13) C-(51) V distances can be quantitatively estimated.
authors.affiliation: Unité de Catalyse et de Chimie du Solide (UCCS), ENSCL, Université de Lille, CNRS UMR 8181, 59652 Villeneuve d'Ascq (France). frederique.pourpoint@ensc-lille.fr.
authors.forename: Frédérique
authors.initials: F
authors.lastname: Pourpoint
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware, DE 19716 (USA).
authors.forename: Jenna
authors.initials: J
authors.lastname: Yehl
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware, DE 19716 (USA).
authors.forename: Mingyue
authors.initials: M
authors.lastname: Li
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware, DE 19716 (USA).
authors.forename: Rupal
authors.initials: R
authors.lastname: Gupta
authors.affiliation: Unité de Catalyse et de Chimie du Solide (UCCS), ENSCL, Université de Lille, CNRS UMR 8181, 59652 Villeneuve d'Ascq (France).
authors.forename: Julien
authors.initials: J
authors.lastname: Trébosc
authors.affiliation: Unité de Catalyse et de Chimie du Solide (UCCS), ENSCL, Université de Lille, CNRS UMR 8181, 59652 Villeneuve d'Ascq (France).
authors.forename: Olivier
authors.initials: O
authors.lastname: Lafon
authors.affiliation: Unité de Catalyse et de Chimie du Solide (UCCS), ENSCL, Université de Lille, CNRS UMR 8181, 59652 Villeneuve d'Ascq (France).|Physics Department & Shanghai Key Laboratory of Magnetic Resonance, East China Normal University, Shanghai 200062 (China).
authors.forename: Jean-Paul
authors.initials: JP
authors.lastname: Amoureux
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware, DE 19716 (USA). tpolenov@udel.edu.
authors.forename: Tatyana
authors.initials: T
authors.lastname: Polenova
keywords: NMR spectroscopy; bioinorganic chemistry; coordination chemistry; density functional calculations; vanadium