Small, beautiful and magnetically exotic: {V4W2}- and {V4W4}-type polyoxometalates

Rasmussen, Maren; Näther, Christian; Leusen, Jan van; Warzok, Ulrike; Schalley, Christoph A.; Kögerler, Paul; Bensch, Wolfgang

doi:10.1039/c6dt02282k

Cited by 8 publications

(5 citation statements)

References 26 publications

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“…The magnetic property analyses of these two V 24 capsules were performed on fresh samples from 2–300 K under a magnetic field of 1 kOe. For V 24 -oct-α, the room temperature χ m T value of 9.23 cm 3 ·K·mol −1 is close to the expected value of 9 cm 3 ·K·mol −1 for 24 spin-only V 4+ centers 50 – 52 . The value increases continuously with decreasing temperature, reaching a maximum of 10.01 cm 3 ·K·mol −1 at 35 K and subsequently decreases sharply to 1.88 cm 3 ·K·mol −1 at 2.0 K. The increase of the value of χ m T upon reduction of the temperature at higher temperatures indicates intramolecular ferromagnetic exchange between neighboring metal ions.…”

Section: Resultssupporting

confidence: 72%

“…Vanadium is of particular interest in this context owing to its various coordination behaviors, valence states, and promising applications in areas such as magnetism 50 – 52 , optics 53 , and catalysis 54 . Currently, the number of known vanadium capsules is limited 55 – 58 and here we report an interesting example of solvent-responsive assembly of coordination nanocapsule quasi-isomers with distinct geometries.…”

Section: Introductionmentioning

confidence: 99%

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Interconvertible vanadium-seamed hexameric pyrogallol[4]arene nanocapsules

Yuan

et al. 2018

Nat Commun

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Research into stimuli-responsive controlled self-assembly and reversible transformation of molecular architectures has received much attention recently, because it is important to understand and reproduce this natural self-assembly behavior. Here, we report two coordination nanocapsules with variable cavities: a contracted octahedral V24 capsule and an expanded ball-shaped V24 capsule, both of which are constructed from the same number of subcomponents. The assemblies of these two V24 capsules are solvent-controlled, and capable of reversible conversion between contracted and expanded forms via control of the geometries of the metal centers by association and dissociation with axial water molecules. Following such structural interconversions, the magnetic properties are significantly changed. This work not only provides a strategy for the design and preparation of coordination nanocapsules with adaptable cavities, but also a unique example with which to understand the transformation process and their structure-property relationships.

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Section: Resultssupporting

confidence: 72%

Section: Introductionmentioning

confidence: 99%

Interconvertible vanadium-seamed hexameric pyrogallol[4]arene nanocapsules

Yuan

et al. 2018

Nat Commun

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“…It is interesting that the VT family had a higher porosity (see Methods, Computer-based calculations and simulations for detailed calculation) than zeolites (Supplementary Table 19), and most of them had over 50% porosity, which was higher than 90% of zeolites, including some widely used zeolites, such as FAU (46.86%), LTA (43.79%), MWW (42.05%), MOR (38.23%), and MFI (31.34%). There are also molecular type VT s, such as V(dien)) 4 [W 2 O 14 ] and V(dien)) 4 [W 4 O 20 ] (dien = diethylenetriamine, C 4 H 13 N 3 ) 30 , and V(dien)) 4 [W 4 O 20 ] is also composed of cubane unit and V ions. Formation energies (Δ H f ) of the zeolitic VT s are lower than those of the molecular type VT s (Supplementary Fig.…”

Section: Resultsmentioning

confidence: 99%

A zeolitic vanadotungstate family with structural diversity and ultrahigh porosity for catalysis

et al. 2018

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Design of the structure and composition of crystalline microporous inorganic oxides is of great importance in catalysis. Developing new zeolites is one approach towards this design because of the tunable pore system and high thermal stability. Zeolites are limited to main group elements, which limits their applications in redox catalysis. Another promising choice is zeolitic transition metal oxides providing both porosity and redox activity, thereby further expanding the diversity of porous materials. However, the examples of zeolitic transition metal oxides are rare. Here, we report a new class of zeolitic vanadotungstates with tunable frameworks exhibiting a large porosity and redox activity. The assembly of [W4O16]8− units with VO2+ forms two isomeric porous frameworks. Owing to the complex redox properties and open porosity, the vanadotungstates efficiently catalyse the selective reduction of NO by NH3. This finding provides an opportunity for design and synthesis of inorganic multifunctional materials for future catalytic applications.

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“…Recent reports indicate that tungstovanadates can exhibit special structural features and properties. − Herein, we provide a new method for the preparation of a novel TRIS-substituted Lindqvist-type hexatungstovanadates [V x W 6– x O 16 (CH 2 O) 3 CR] ( x −1)– [ x = 3 or 4; R = CH 3 ( 1 ; CCDC 2027592) or CH 2 OH ( 2 ; CCDC 2027593)]. These compounds were synthesized by a simple one-pot reaction in an aqueous solution with simple vanadate, tungstate salts, and TRIS ligands under mild conditions.…”

mentioning

confidence: 99%

A New Family of Polyoxometalates: Tris-functionalized Lindqvist-Type Hexatungstovanadates

et al. 2021

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We successfully designed and obtained a new family of polyoxometalates (POMs) containing mixed-metal elements and a trialkoxyl (TRIS) ligand via a very simple one-pot process under mild condition. Single-crystal X-ray diffraction revealed that this family belongs to compact Lindqvist-type hexatungstovanadates. In particular, the hydroxyl-containing product can be further functionalized through esterification. Not only does this work open a broad door for unusual POM clusters involving vanadium and tungsten atoms in the future, but also the design concept of this work also provides new insight for the synthesis and further exploration of POMs.

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Small, beautiful and magnetically exotic: {V₄W₂}- and {V₄W₄}-type polyoxometalates

Cited by 8 publications

References 26 publications

Interconvertible vanadium-seamed hexameric pyrogallol[4]arene nanocapsules

Interconvertible vanadium-seamed hexameric pyrogallol[4]arene nanocapsules

A zeolitic vanadotungstate family with structural diversity and ultrahigh porosity for catalysis

A New Family of Polyoxometalates: Tris-functionalized Lindqvist-Type Hexatungstovanadates

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