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The fascinating polyoxometalates

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Abstract

After touching the history of polyoxometalate (POM) chemistry, the basics of isopolyoxometalates (IPOM) and heteropolyoxometalates (HPOM) are discussed. The main focus is placed on molybdenum- and tungsten-containing IPOM and HPOM. The HPOM are presented based on the coordination of the ‘hetero’atom: tetrahedral (Keggin and Wells–Dawson structures, including their lacunary and mixed anions, Preyssler-Pope-Jeannin polyanion), octahedral (Anderson-Evans structure), square-prismatic (Peacock-Weakley sandwiches) and icosahedral (Dexter-Silverton structure). Subsequently the specifics of polyoxocations (POC) are highlighted, examples of naturally occurring HPOM are given and the nomenclature of POM is discussed. In conclusion, selected applications are presented.

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Notes

  1. The ionic strength I is an expression of the effect of ions in solution on the electrostatic potential. I is defined by \(I = 0.5\Sigma{cz^2}\), where c is the molar concentration of the ion and z its charge.

  2. A net ionic equation presents only the ions that are changed during the course of the reaction, while the complete ionic equation also includes the spectator ions. The net ionic equation can be easily compiled by balancing the overall charge and the molecular equation can be readily derived from it. Chemical equations provide an invaluable guideline for the successful preparation of a compound.

  3. The Patterson function is used to solve the phase problem in X-ray crystallography. It was introduced in 1934 by the pioneering British X-ray crystallographer Arthur Lindo Patterson (1902–1966).

  4. The utilized ammonium paratungstate tetrahydrate from Global Tungsten & Powders Corp. (GTP), Towanda, USA was characterized in detail in [55]. As followed from TG and ammonia analyses the crystal water content amounted to 2.9 mol. The formula (NH4)10[H2W12O42]·2.9H2O (APT·2.9H2O) was used throughout this study. The structure of APT·4H2O ‘tolerates’ the deficit of 1.1 mol H2O without any structural changes.

  5. The Swiss chemist Jean Charles Galissard de Marignac published his articles under ‘M.C. Marignac’. It should be noted that ‘M’ stands for ‘Monsieur’ and is not the initial of one of his given names.

  6. The Schoenflies symbol, named after the German mathematician Arthur Moritz Schoenflies (1853–1928), is a system of symbols used to specify the 32 crystallographic point groups. Because a point group is completely adequate to describe the symmetry of a molecule, this notation is often sufficient and commonly used in the field of molecular spectroscopy.

  7. Water glass, also called liquid glass, is the common name for an aqueous solution of either sodium or potassium silicate, because it is essentially silicon dioxide, SiO2, in water.

  8. Trivacant Keggin anions are characterized by two types. Type A: Three adjacent metal atoms belonging to three different {W3O13} groups have been taken away. Type B: A complete {M3O13} group has been removed from the intact Keggin anion.

  9. The name icosahedron comes from Greek εἴκοσι (eíkosi), meaning 'twenty', and ἕδρα(hédra), meaning 'seat'. The icosahedron with 20 equilateral triangles is one of the so-called Platonic solids, which are constructed by congruent convex regular polygons with the same number of faces meeting at each vertex. Five solids meet these criteria: tetrahedron (4), cube (6), octahedron (8), dodecahedron (12), and icosahedron (20).

  10. A chemical garden is an experiment usually performed by adding metal salts such as CuSO4 or CoCl2 to an aqueous solution of water glass (cf. footnote 7). It results in the growth of colored plant-like forms in minutes to hours. The chemical garden was first observed and described by German/Dutch alchemist and chemist Johann Rudolf Glauber (1604–1670) in 1646.

  11. Mohs scale of mineral hardness. https://en.wikipedia.org/wiki/Mohs_scale_of_mineral_hardness (Accessed May 29, 2021).

  12. In naming a complex wherein a single atom bridges two metals, the bridging ligand is preceded by the Greek character μ, with a subscript or superscript number denoting the number of metals bound to the bridging ligand.

Abbreviations

aka:

Also known as

AMT:

Ammonium metatungstate

APT:

Ammonium paratungstate

CID:

Collision-induced dissociation

DSC:

Differential scanning calorimetry

DTG:

Differential thermal gravimetry

EPR:

Electron paramagnetic resonance, aka ESR (electron spin resonance)

ESI–MS:

Electrospray ionization mass spectrometry

FT-IR:

Fourier-transform infrared spectroscopy

GTP:

Global Tungsten and Powders Corp.

HPOM:

Heteropolyoxometalate(s)

HPOMo:

Heteropolyoxomolybdate(s)

HPOT:

Heteropolyoxotungstate(s)

IPOM:

Isopolyoxometalate(s)

IPOMo:

Isopolyoxomolybdate(s)

IPOT:

Isopolyoxotungstate(s)

μM:

Micromolar (1 μM = 10–6 M)

MAS-NMR:

Magic angle spinning nuclear magnetic resonance

MS:

Mass spectrometry/mass spectrometer

NMR:

Nuclear magnetic resonance

pm:

1 picometer = 0.01 Å = 10–10 cm = 10–12 m

PMB:

Phosphomolybdenum blue

POC:

Polyoxocation(s)

POM:

Polyoxometalate(s)

SEM:

Scanning electron microscopy

SMM:

Single-molecule magnet

TBO:

Tungsten blue oxide

TG:

Thermal gravimetry

UV/Vis:

Ultraviolet/visible spectroscopy

XPS:

X-ray photoelectron spectroscopy

XRD:

X-ray diffraction

Z :

Atomic number (Periodic Table); Number of formula units in a unit cell

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Acknowledgments

We thank Martin Fait, Ulrich Kortz and particularly Fritz Scholz for their helpful suggestions. Our special thanks go to Ralf T. Schmitt from Museum für Naturkunde in Berlin for providing Figs. 17, 18 as well as to Ann E. Benbow from Mineralogical Society of America for providing Figs. 19, 20.

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  1. Markkleeberg, Germany

    Hans-Joachim Lunk

  2. Institute of Chemistry and Biochemistry, Inorganic Chemistry, Freie Universität Berlin, Fabeckstr. 34/36, 14195, Berlin, Germany

    Hans Hartl

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Lunk, HJ., Hartl, H. The fascinating polyoxometalates. ChemTexts 7, 26 (2021). https://doi.org/10.1007/s40828-021-00145-y

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