Trapping ionic dimers of dinuclear peroxido mandelato complexes of vanadium(V) into cavities constructed from \u0394- and \u039b-[Ni(phenanthroline)3]2+ cations: a precursor to Ni(VO3)2

Mária Šimuneková,Róbert Gyepes,Peter Schwendt,Lukáš Krivosudský

doi:10.1007/s11243-019-00344-0

Mária Šimuneková, Róbert Gyepes + Show 2 more

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https://doi.org/10.1007/s11243-019-00344-0

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Abstract

A nickel‒vanadium metal–organic hybrid compound [Ni(phen)3]2[(V2O2(O2)2((S)-mand)2)][(V2O2(O2)2((R)-mand)2)]·18H2O (phen = 1,10-phenanthroline, mand2− = mandelato(2−) ligand, C6H5–CO–COO2−) (1) was prepared and characterized by spectral methods, X-ray structure analysis and simultaneous DTA and TG measurements. The crystal structure of 1 contains both Δ and Λ enantiomers of the [Ni(phen)3]2+ cations that construct sandwich layers along the crystallographic axis c, in between which sit the vanadium(V) complex anions. These are present as ionic dimers in the form of a robust {[(V2O2(O2)2((S)-mand)2)][(V2O2(O2)2((R)-mand)2)]}4− species. The two individual anions are coupled by a pair of weak, yet significant attractions between two vanadium atoms and two peroxido ligands of the adjacent anion at V‒O distances 2.660 Å. The 51V NMR spectrum of the compound in DMSO solution revealed a complicated course of decomposition reactions of the anion, which led to formation of the [(V2O4(S,R-mand)2]2− anion as a single product. The metal–organic hybrid compound 1 is converted by thermal decomposition into a potential anode material for lithium-ion batteries Ni(VO3)2.

Highlights

Nickel vanadates and nickel–vanadium metal‒organic hybrid compounds have attracted considerable attention because of their physical and chemical properties, which facilitate technological applications in various fields of materials science
Transition Metal Chemistry (2019) 44:747–754 group of vanadium compounds providing an advantage of relatively low temperatures required for the release of the oxygen atoms of the peroxide group and combustion of the organic components, new precursors for possible preparation of nickel vanadates are of current interest
We have reported on transition metal–vanadium compounds, comprised of the combinations Mn–V [20], Fe–V, Ni–V [21, 22] and Cu–V [23,24,25,26,27,28,29] that were investigated mostly for their chiral properties

Summary

Introduction

Nickel vanadates and nickel–vanadium metal‒organic hybrid compounds have attracted considerable attention because of their physical and chemical properties, which facilitate technological applications in various fields of materials science. Transition Metal Chemistry (2019) 44:747–754 group of vanadium compounds providing an advantage of relatively low temperatures required for the release of the oxygen atoms of the peroxide group and combustion of the organic components (usually 100–300 °C), new precursors for possible preparation of nickel vanadates are of current interest. Thermal decomposition of vanadium peroxido complexes with transition metal cations has been utilized for the synthesis of other vanadates, such as Zn(VO3) and Cu(VO3)2 [24]. In continuation of our studies on stereochemistry of vanadium(V) complexes, we present here the synthesis and characterization of [Ni(phen)3]2[(V2O2(O2)2((S)-mand)2)] [(V2O2(O2)2((R)-mand)2)]·18H2O (phen = 1,10-phenanthroline, mand2− = mandelato(2−), C6H5–CO–COO2−)

Materials and methods

Results and discussion

Conclusion