Atomically precise vanadium-oxide clusters

Chakraborty, Sourav; Petel, Brittney E.; Schreiber, Eric; Matson, Ellen M.

doi:10.1039/d0na00877j

Cited by 48 publications

(41 citation statements)

References 238 publications

(380 reference statements)

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“…The peripheral morphology of POMs resembles the surface of RMOs, with alternating terminal and bridging oxygen atoms composing the surface of the assembly. 12 − 16 However, unlike bulk solids, POMs exhibit solubility in organic and aqueous solution, rendering these clusters amenable to analysis using analytical techniques reserved for homogeneous systems. Given the relevance of POMs as homogeneous models for bulk systems, there has been great interest in understanding the role of cations in mediating the electrochemical properties of these assemblies.…”

Section: Introductionmentioning

confidence: 99%

Charge-State Dependence of Proton Uptake in Polyoxovanadate-alkoxide Clusters

2022

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Here, we present an investigation of the thermochemistry of proton uptake in acetonitrile across three charge states of a polyoxovanadate-alkoxide (POV-alkoxide) cluster, [V 6 O 7 (OMe) 12 ] n ( n = 2–, 1–, and 0). The vanadium oxide assembly studied features bridging sites saturated by methoxide ligands, isolating protonation to terminal vanadyl moieties. Exposure of [V 6 O 7 (OMe) 12 ] n to organic acids of appropriate strength results in the protonation of a terminal V=O bond, generating the transient hydroxide-substituted POV-alkoxide cluster [V 6 O 6 (OH)(OMe) 12 ] n +1 . Evidence for this intermediate proved elusive in our initial report, but here we present the isolation of a divalent anionic cluster that features hydrogen bonding to dimethylammonium at the terminal oxo site. Degradation of the protonated species results in the formation of equimolar quantities of one-electron-oxidized and oxygen-atom-efficient complexes, [V 6 O 7 (OMe) 12 ] n +1 and [V 6 O 6 (OMe) 12 ] n +1 . While analogous reactivity was observed across the three charge states of the cluster, a dependence on the acid strength was observed, suggesting that the oxidation state of the vanadium oxide assembly influences the basicity of the cluster surface. Spectroscopic investigations reveal sigmoidal relationships between the acid strength and cluster conversion across the redox series, allowing for determination of the proton affinity of the surface of the cluster in all three charge states. The fully reduced cluster is found to be the most basic, with higher oxidation states of the assembly possessing substantially reduced proton affinities (∼7 p K a units per electron). These results further our understanding of the site-specific reactivity of terminal M=O bonds with protons in an organic solvent, revealing design criteria for engineering functional surfaces of metal oxide materials of relevance to energy storage and conversion.

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Section: Introductionmentioning

confidence: 99%

Charge-State Dependence of Proton Uptake in Polyoxovanadate-alkoxide Clusters

2022

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“…A large library of molecular ligand-stabilized transition metal nanoclusters exists, which are solution processable and have discrete chemical compositions. [14][15][16][17] Although the vast majority are not catalytically competent, they contribute important insights into the physicochemical processes that underpin the catalytic interface between active site and support. Select examples include clusters with inorganic [Fe4(μ4-O)], [RuCo3(μ3-O)4], and [Fe4(µ3-S)4] cores, wherein metalbound oxo and nitrenoid substituents are stabilized by coordinative and electronic participation of a polymetallic support, [18][19][20] and a series of trinuclear [Fe3] and [Cr3] clusters in which electronic coupling between the metal centers facilitates cooperative, multi-site reactivity.…”

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confidence: 99%

Multi-active Site Dynamics on a Molecular Cr/Co/Se Cluster Catalyst

Kephart

Mitchell

Kaminsky

et al. 2022

Preprint

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This study provides detailed insights into the interconnected reactivity of the three catalytically active sites of an atomically precise nanocluster Cr3(py)3Co6Se8L6 (Cr3(py)3, L = Ph2PNTol–, Ph = phenyl, Tol = 4-tolyl). Catalytic and stoichiometric studies into tosyl azide activation and carbodiimide formation enabled the isolation and crystallographic characterization of key metal-nitrenoid catalytic intermediates, including the tris(nitrenoid) cluster Cr3(NTs)3, the catalytic resting state Cr3(NTs)3(CNtBu)3, and the mono(nitrenoid) cluster Cr3(NTs)(CNtBu)2. Nitrene transfer proceeds via a stepwise mechanism, with the three active sites engaging sequentially to produce carbodiimide. Comparative structural analysis and CNtBu bind-ing studies reveal that the chemical state of neighboring active sites regulates the affinity for substrates of an individual Cr-nitrenoid edge site, intertwining their reactivity through the inorganic support.

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“…[4] Due to their well-defined structures, they can be leveraged as molecular analogues of solid-state metal oxides. [5] Additionally, their versatile electrochemistry and controlled tuneability make POMs valuable materials for energy conversion and storage, [6,7] (photo-)catalysis [8,9] as well as molecular electronics and spintronics. [10,11] While initial work has mainly been focused on molybdenum-and tungsten-based clusters, polyoxovanadates (POVs) have gained more attention in the past decades.…”

Section: Introductionmentioning

confidence: 99%

“…POMs are anionic metal oxide clusters of the early transition metals (often W, Mo and V) in their high oxidation states, formed by self‐assembly in solution [4] . Due to their well‐defined structures, they can be leveraged as molecular analogues of solid‐state metal oxides [5] . Additionally, their versatile electrochemistry and controlled tuneability make POMs valuable materials for energy conversion and storage, [6, 7] (photo‐)catalysis [8, 9] as well as molecular electronics and spintronics [10, 11] …”

Section: Introductionmentioning

confidence: 99%

A General Access Route to High‐Nuclearity, Metal‐Functionalized Molecular Vanadium Oxides

et al. 2022

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Molecular metal oxides are key materials in diverse fields like energy storage and conversion, molecular magnetism and as model systems for solid-state metal oxides. To improve their performance and increase the variety of accessible motifs, new synthetic approaches are necessary. Herein, we report a universal, new precursor to access different metal-functionalized polyoxovanadate (POV) clusters. The precursor is synthesized by a novel solid-state thermal treatment procedure. Solution-phase test reactions at room temperature and pressure show that reaction of the precursor with various metal nitrate salts gives access to a range of metal-functionalized POVs. The first nitrate-templated molecular calcium vanadate cluster is reported. We show that this precursor could open new access routes to POV components for molecular magnetism, energy technologies or catalysis.

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Atomically precise vanadium-oxide clusters

Abstract: Polyoxovanadate (POV) clusters are an important subclass of polyoxometalates with a broad range of molecular compositions and physicochemical properties.

Cited by 48 publications

References 238 publications

Charge-State Dependence of Proton Uptake in Polyoxovanadate-alkoxide Clusters

Charge-State Dependence of Proton Uptake in Polyoxovanadate-alkoxide Clusters

Multi-active Site Dynamics on a Molecular Cr/Co/Se Cluster Catalyst

A General Access Route to High‐Nuclearity, Metal‐Functionalized Molecular Vanadium Oxides

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