Synthesis and characterization of a mixed-valence hexadecavanadate cluster with half-open framework

Chen, Lian; Jiang, Feilong; Li, Ning; Yan, Chunfeng; Xu, Wentao; Hong, Maochun

doi:10.1016/j.inoche.2008.12.021

Cited by 10 publications

(2 citation statements)

References 44 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The unresolved central absorption suggests magnetic interactions (which could be of exchange and/or dipolar) between neighbouring paramagnetic ions, [31] in agreement with the possible presence of more than one V IV centre in the formed POV. Globally, the EPR behaviour of our system is similar to that of other mixed-valence POVs, [32][33][34][35] all characterized by a large and not resolved resonance around g ~2.…”

supporting

confidence: 69%

Non‐Covalent and Covalent Binding of New Mixed‐Valence Cage‐like Polyoxidovanadate Clusters to Lysozyme

Tito,

Ferraro,

Pisanu

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

The high‐resolution X‐ray structures of the model protein lysozyme in the presence of the potential drug [VIVO(acetylacetonato)2] from crystals grown in 1.1 M NaCl, 0.1 M sodium acetate at pH 4.0 reveal the binding to the protein of different and unexpected mixed‐valence cage‐like polyoxidovanadates (POVs): [V15O36(OH2)]5–, which non‐covalently interacts with the lysozyme surface, [V15O33(OH2)]+ and [V20O51(OH2)]n– (this latter based on an unusual {V18O43} cage) which covalently bind the protein. EPR spectroscopy confirms the partial oxidation of VIV to VV and the formation of mixed‐valence species. The results indicate that the interaction with proteins can stabilize the structure of unexpected – both for dimension and architecture – POVs, not observed in aqueous solution.

show abstract

supporting

confidence: 69%

Non‐Covalent and Covalent Binding of New Mixed‐Valence Cage‐like Polyoxidovanadate Clusters to Lysozyme

Tito,

Ferraro,

Pisanu

et al. 2024

Angewandte Chemie

View full text Add to dashboard Cite

show abstract

“…These observations provide guidelines for fine-tuning the POV-surrounding (counterions and solvent molecules) relationships in solution as well as for the adjustment of the molecular adsorption on surfaces, which furthermore may open doors for potential photoluminescent effects 84,85 of POV particles on a solid support. This is worth further exploring because we have shown that the electronic structure of adsorbed POVs on the metallic surface undergoes redox modifications by the alteration of the molecule concentrationmodulated surface coverage.…”

Section: ■ Conclusionmentioning

confidence: 90%

Molecular Characteristics of a Mixed-Valence Polyoxovanadate {V^IV/V₁₈O₄₂} in Solution and at the Liquid–Surface Interface

et al. 2017

View full text Add to dashboard Cite

The understanding of the molecular state of vanadium-oxo clusters (polyoxovanadates, POVs) in solution and on surface is a key to their target application in catalysis as well as molecular electronics and spintronics. We here report the results of a combined experimental and computational study of the behavior of nucleophilic polyoxoanions [V IV 10 V V 8 O 42 (I)] 5− charged balanced by Et 4 N + in water, in a one-phase organic solution of N,N-dimethylformamid (DMF) or acetonitrile (MeCN), in a mixed solution of MeCN−water, and at the hybrid liquid−surface interface. The molecular characteristics of the compound (NEt 4 ) 5 [V 18 O 42 (I)] (1) in the given environments were studied by microspectroscopic, electrochemical, scattering, and molecular mechanics methods. Contrary to the situation in pure water, where we observe great agglomeration with a number of intercalated H 2 O molecules between POVs that are surrounded by the Et 4 N + ions, no or only minor agglomeration of redox-active POVs in an unprecedented cation-mediated fashion was detected in pure DMF and MeCN, respectively. An inclusion of 1% water in the MeCN solution does not have an effect significant enough to reinforce agglomeration; however, this leads to the POV•••POV interface characterized by the presence of the Et 4 N + ions and a small number of H 2 O molecules. Water amounts of ≥5% trigger the formation of higher oligomers. The deposition of compound 1 from MeCN onto an Au(111) surface affords nearly roundshaped particles (∼10 nm). The use of DMF instead of MeCN results in bigger, irregularly shaped particles (∼30 nm). This change of solvent gives rise to more extensive intermolecular interactions between polyoxoanions and their countercations as well as weaker binding of ion-pairing induced agglomerates to the metallic substrate. Lower concentration of adsorbed molecules leads to a submonolayer coverage and an accompanied change of the POV's redox state, whereas their higher concentration results in a multilayer coverage that offers the pristine mixed-valence structure of the polyoxoanion. Our study provides first important insights into the reactivity peculiarities of this redox-responsive material class on a solid support.

show abstract

Non‐Covalent and Covalent Binding of New Mixed‐Valence Cage‐like Polyoxidovanadate Clusters to Lysozyme

Tito,

Ferraro,

Pisanu

et al. 2024

Angew Chem Int Ed

View full text Add to dashboard Cite

show abstract

Synthesis and characterization of a mixed-valence hexadecavanadate cluster with half-open framework

Cited by 10 publications

References 44 publications

Non‐Covalent and Covalent Binding of New Mixed‐Valence Cage‐like Polyoxidovanadate Clusters to Lysozyme

Non‐Covalent and Covalent Binding of New Mixed‐Valence Cage‐like Polyoxidovanadate Clusters to Lysozyme

Molecular Characteristics of a Mixed-Valence Polyoxovanadate {V^IV/V₁₈O₄₂} in Solution and at the Liquid–Surface Interface

Non‐Covalent and Covalent Binding of New Mixed‐Valence Cage‐like Polyoxidovanadate Clusters to Lysozyme

Contact Info

Product

Resources

About

Synthesis and characterization of a mixed-valence hexadecavanadate cluster with half-open framework

Cited by 10 publications

References 44 publications

Non‐Covalent and Covalent Binding of New Mixed‐Valence Cage‐like Polyoxidovanadate Clusters to Lysozyme

Non‐Covalent and Covalent Binding of New Mixed‐Valence Cage‐like Polyoxidovanadate Clusters to Lysozyme

Molecular Characteristics of a Mixed-Valence Polyoxovanadate {VIV/V18O42} in Solution and at the Liquid–Surface Interface

Non‐Covalent and Covalent Binding of New Mixed‐Valence Cage‐like Polyoxidovanadate Clusters to Lysozyme

Contact Info

Product

Resources

About

Molecular Characteristics of a Mixed-Valence Polyoxovanadate {V^IV/V₁₈O₄₂} in Solution and at the Liquid–Surface Interface