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Asymmetric dinuclear, hexanuclear and octanuclear oxovanadium citrates with triazolates: novel mixed-ligands and mixed-valence complexes.
- Source :
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Dalton Transactions: An International Journal of Inorganic Chemistry . 1/7/2024, Vol. 53 Issue 1, p186-195. 10p. - Publication Year :
- 2024
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Abstract
- The triazolate-assisted asymmetric dinuclear oxovanadium(IV) citrate [V2O2(cit)(Hdatrz)3]·5H2O (1, H4cit = citric acid, Hdatrz = 1H-1,2,4-triazole-3,5-diamine) and its additive salt [V2O2(cit)(Hdatrz)3][V2O2(cit)2]½·2H2datrz·9.5H2O (2) and the polymerized hexanuclear product [V6O6(μ3-O)2(cit)2(Hdatrz)4]·4H2O (3) have been isolated at different temperatures, respectively. Adduct 2 shows strong evidence for the conversion of a symmetric dinuclear oxovanadium(IV) citrate to a mixed-ligand asymmetric oxovanadium(IV) citrate. Moreover, a fully oxidized trinuclear vanadium(V) species [V3O6(μ2-OH)(μ3-O)(Hdatrz)2]·4.5H2O (4) has also been isolated as a quasi-intermediate product of 3 without the coordination of citrate. Intriguingly, an octanuclear mixed-valence oxovanadium(V / IV) citrate K2{[V IV/V2 O2(cit)(Hdatrz)(datrz)]2[V IV2 O2(cit)(Hdatrz)(datrz)]2}·27.5H2O (5) has been obtained with different vanadium units, where dinuclear mixed-ligands and mixed-valence oxovanadium(IV / V) citrates [V IV/V2 O2(cit)(Hdatrz)(datrz)] (5a) and [V IV2 O2(cit)(Hdatrz)(datrz)] (5b) have been trapped. Citrate adopts a μ2-η1:η1:η1:η2 coordination mode in 1, 2 and 5, while a μ3-η1:η1:η1:η2 fashion has been observed in 3. Unlike 1–4, complex 5 contains both protonated and deprotonated triazolates simultaneously, where four triazolates further coordinate in a μ3-η1:η1:η1 manner to construct an octanuclear unit. These different structural features in 1–5 are dominated by flexible multidentate citrates and protonated/deprotonated triazolates, showing their synergistic effects. Furthermore, 1 exhibits a rectangular channel, showing preferential adsorption of O2 and CO2 over gases N2, H2, and CH4. [ABSTRACT FROM AUTHOR]
- Subjects :
- *CITRATES
*CITRIC acid
*METAL-metal bonds
*DIAMINES
*VANADIUM
Subjects
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 53
- Issue :
- 1
- Database :
- Academic Search Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 174293673
- Full Text :
- https://doi.org/10.1039/d3dt03445c