Rational synthesis of elusive organic–inorganic hybrid metal-oxo clusters: formation and post-functionalization of hexavanadates

Marcano, David E. Salazar; Kalandia, Givi; Hecke, Kristof Van; Parac‐Vogt, Tatjana N.

doi:10.1039/d3sc00038a

Cited by 4 publications

(2 citation statements)

References 70 publications

(130 reference statements)

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“…Hybrid organic-inorganic polyoxometalate (POM) compounds 7,8 combine a discrete, nanosized metal-oxo core exhibiting rich redox chemistry and catalytic activity with an organic environment that does not only stabilize these molecular metal oxides and improves their solubility in various media, but can also empower the physicochemical properties to the POM due to synergistic effects. Organic ligation serves as a platform for functionalization and post-functionalization strategies, [9][10][11][12] providing chemists with the ability to tailor a wide variety of molecular architectures. The latter include numerous conjugates with biological molecules.…”

Section: Introductionmentioning

confidence: 99%

Bioorthogonal chemistry of polyoxometalates – challenges and prospects

Petrovskii,

Grachova,

Monakhov

2024

Chem. Sci.

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Section: Introductionmentioning

confidence: 99%

Bioorthogonal chemistry of polyoxometalates – challenges and prospects

Petrovskii,

Grachova,

Monakhov

2024

Chem. Sci.

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“…Hybrid organic−inorganic polyoxometalate (POM) compounds 7,8 combine a discrete, nanosized metal−oxo core exhibiting rich redox chemistry and catalytic activity with an organic environment that does not only stabilizes these molecular metal oxides and improves their solubility in various media, but can also empower the physicochemical properties to the POM due to synergistic effects. Organic ligation serves as a platform for functionalization and postfunctionalization strategies, [9][10][11][12] providing chemists with the ability to tailor a wide variety of molecular architectures. The latter include numerous conjugates with biological molecules.…”

Section: Introductionmentioning

confidence: 99%

Bioorthogonal Chemistry of Polyoxometalates – Challenges and Prospects

Petrovskii,

Grachova,

Monakhov

2023

Preprint

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Bioorthogonal chemistry enabled scientists to carry out controlled chemical processes in high yields in vivo while minimizing hazardous effects. Its extension to the field of polyoxometalates (POMs) could open up new possibilities and new applications in molecular electronics, sensing and catalysis, including inside living cells. However, this comes with many challenges that need to be addressed to effectively implement and exploit bioorthogonal reactions in the chemistry of POMs. In particular, how to protect POMs from the biological environment but make their reactivity selective towards specific bioorthogonal tags (and thereby reduce their toxicity), as well as which bioorthogonal chemistry protocols are suitable for POMs and how reactions can be carried out are questions that we are exploring herein. This Perspective conceptualizes and discusses advances in the supramolecular chemistry of POMs, their click chemistry, and POM-based surface engineering to develop innovative bioorthogonal approaches tailored to POMs and improve POM biological tolerance.

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Boosting Oxygen Reduction Reaction Selectivity in Metal Nanoparticles with Polyoxometalates

Quirós‐Díez,

Herreros‐Lucas,

Vila‐Fungueiriño

et al. 2024

Small Methods

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The lack of selectivity toward the oxygen reduction reaction (ORR) in metal nanoparticles can be linked to the generation of intermediates. This constitutes a crucial constraint on the performance of specific electrochemical devices, such as fuel cells and metal–air batteries. To boost selectivity of metal nanoparticles, a novel methodology that harnesses the unique electrocatalytic properties of polyoxometalates (POM) to scavenge undesired intermediates of the ORR (such as HO2−) promoting selectivity is proposed. It involves the covalent functionalization of metal nanoparticle's surface with an electrochemically active capping layer containing a new sulfur‐functionalized vanadium‐based POM (AuNP@POM). To demonstrate this approach, preformed thiolate Au(111) nanoparticles with a relatively poor ORR selectivity are chosen. The dispersion of AuNP@POM on the surface of carbon nanofibers (CNF) enhances oxygen diffusion, and therefore the ORR activity. The resulting electrocatalyst (AuNP@POM/CNF) exhibits superior stability against impurities like methanol and a higher pH tolerance range compared to the standard commercial Pt/C. The work demonstrates for the first time, the use of a POM‐based electrochemically active capping layer to switch on the selectivity of poorly selective gold nanoparticles, offering a promising avenue for the preparation of electrocatalyst materials with improved selectivity, performance, and stability for ORR‐based devices.

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Rational synthesis of elusive organic–inorganic hybrid metal-oxo clusters: formation and post-functionalization of hexavanadates

Abstract: Paving the way towards new functional materials relies increasingly on the challenging task of forming organic-inorganic hybrid compounds. In that regard, discrete atomically-precise metal-oxo nanoclusters have received increasing attention due...

Cited by 4 publications

References 70 publications

Bioorthogonal chemistry of polyoxometalates – challenges and prospects

Bioorthogonal chemistry of polyoxometalates – challenges and prospects

Bioorthogonal Chemistry of Polyoxometalates – Challenges and Prospects

Boosting Oxygen Reduction Reaction Selectivity in Metal Nanoparticles with Polyoxometalates

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