New structures based on the mixed valence polyoxometalate cluster [V 12B18O60H6]n-

Patricio Hermosilla-Ibáñez, Pierre Emmanuel Car, Andrés Vega, Juan Costamagna, Francesco Caruso, Jean Yves Pivan, Eric Le Fur, Evgenia Spodine, Diego Venegas-Yazigi

Resultado de la investigación: Article

23 Citas (Scopus)

Resumen

Hydrothermal synthesis was used to obtain four new crystalline lattices derived from the functionalization of the [V12B18O 60H6]n- cluster: Na8(H 3O){[Ni(H2O)5][V12B 18O60H6]}·12.5H2O (1), Na5 (H3O)4{[Ni (H2O) 3(en)][V12B18O60H 6]}·9H2O (2), and Na9(H 3O){Zn0.5[V12B18O60H 6]}·11H2O (3), [Hen][H2en]{[Zn(en) 2]3 [V12B18O60H 6]}·3H2O (4). All four compounds crystallize in the space group C2/c. Compounds (1) (2) and (4) are 0D species, while for (3) there is some degree of covalent connectivity between the anionic units, due to the presence of ZnII cations with partial occupation between them. On the basis of structural data and BVS calculations, these functionalized cluster species present mixed-valence ratios of 11VIV/1VV for (1), (2) and (3) and 9VIV/3VV for compound (4). Compounds (1), (2) and (3) present sodium and hydronium ions in the crystalline lattice, while protonated ethylenediamine is observed in compound (4). These cations balance the negative charge of the corresponding clusters and stabilize the crystalline lattice by electrostatic interactions. In the studied compounds, NiII ions coordinate to the vanadyl oxygen atoms, whereas the ZnII cations coordinate both to the vanadyl oxygen atoms and to the oxygen atoms bonded to boron centres. The electronic spectra in the low energy range are dominated by the IVCT phenomenon, since the functionalization of the cluster [V12B18O60H6]n- by different transition metal ions does not affect the observed absorption bands.

Idioma originalEnglish
Páginas (desde-hasta)5604-5612
Número de páginas9
PublicaciónCrystEngComm
Volumen14
N.º17
DOI
EstadoPublished - 7 sep 2012

Huella dactilar

Crystal lattices
Cations
ethylenediamine
Vanadates
Positive ions
Oxygen
Crystalline materials
valence
oxygen atoms
Atoms
cations
Boron
Hydrothermal synthesis
Ions
hydronium ions
Coulomb interactions
Transition metals
Metal ions
Absorption spectra
Sodium

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Citar esto

Hermosilla-Ibáñez, P., Car, P. E., Vega, A., Costamagna, J., Caruso, F., Pivan, J. Y., ... Venegas-Yazigi, D. (2012). New structures based on the mixed valence polyoxometalate cluster [V 12B18O60H6]n-. CrystEngComm, 14(17), 5604-5612. https://doi.org/10.1039/c2ce25436k
Hermosilla-Ibáñez, Patricio ; Car, Pierre Emmanuel ; Vega, Andrés ; Costamagna, Juan ; Caruso, Francesco ; Pivan, Jean Yves ; Fur, Eric Le ; Spodine, Evgenia ; Venegas-Yazigi, Diego. / New structures based on the mixed valence polyoxometalate cluster [V 12B18O60H6]n-. En: CrystEngComm. 2012 ; Vol. 14, N.º 17. pp. 5604-5612.
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title = "New structures based on the mixed valence polyoxometalate cluster [V 12B18O60H6]n-",
abstract = "Hydrothermal synthesis was used to obtain four new crystalline lattices derived from the functionalization of the [V12B18O 60H6]n- cluster: Na8(H 3O){[Ni(H2O)5][V12B 18O60H6]}·12.5H2O (1), Na5 (H3O)4{[Ni (H2O) 3(en)][V12B18O60H 6]}·9H2O (2), and Na9(H 3O){Zn0.5[V12B18O60H 6]}·11H2O (3), [Hen][H2en]{[Zn(en) 2]3 [V12B18O60H 6]}·3H2O (4). All four compounds crystallize in the space group C2/c. Compounds (1) (2) and (4) are 0D species, while for (3) there is some degree of covalent connectivity between the anionic units, due to the presence of ZnII cations with partial occupation between them. On the basis of structural data and BVS calculations, these functionalized cluster species present mixed-valence ratios of 11VIV/1VV for (1), (2) and (3) and 9VIV/3VV for compound (4). Compounds (1), (2) and (3) present sodium and hydronium ions in the crystalline lattice, while protonated ethylenediamine is observed in compound (4). These cations balance the negative charge of the corresponding clusters and stabilize the crystalline lattice by electrostatic interactions. In the studied compounds, NiII ions coordinate to the vanadyl oxygen atoms, whereas the ZnII cations coordinate both to the vanadyl oxygen atoms and to the oxygen atoms bonded to boron centres. The electronic spectra in the low energy range are dominated by the IVCT phenomenon, since the functionalization of the cluster [V12B18O60H6]n- by different transition metal ions does not affect the observed absorption bands.",
author = "Patricio Hermosilla-Ib{\'a}{\~n}ez and Car, {Pierre Emmanuel} and Andr{\'e}s Vega and Juan Costamagna and Francesco Caruso and Pivan, {Jean Yves} and Fur, {Eric Le} and Evgenia Spodine and Diego Venegas-Yazigi",
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Hermosilla-Ibáñez, P, Car, PE, Vega, A, Costamagna, J, Caruso, F, Pivan, JY, Fur, EL, Spodine, E & Venegas-Yazigi, D 2012, 'New structures based on the mixed valence polyoxometalate cluster [V 12B18O60H6]n-', CrystEngComm, vol. 14, n.º 17, pp. 5604-5612. https://doi.org/10.1039/c2ce25436k

New structures based on the mixed valence polyoxometalate cluster [V 12B18O60H6]n-. / Hermosilla-Ibáñez, Patricio; Car, Pierre Emmanuel; Vega, Andrés; Costamagna, Juan; Caruso, Francesco; Pivan, Jean Yves; Fur, Eric Le; Spodine, Evgenia; Venegas-Yazigi, Diego.

En: CrystEngComm, Vol. 14, N.º 17, 07.09.2012, p. 5604-5612.

Resultado de la investigación: Article

TY - JOUR

T1 - New structures based on the mixed valence polyoxometalate cluster [V 12B18O60H6]n-

AU - Hermosilla-Ibáñez, Patricio

AU - Car, Pierre Emmanuel

AU - Vega, Andrés

AU - Costamagna, Juan

AU - Caruso, Francesco

AU - Pivan, Jean Yves

AU - Fur, Eric Le

AU - Spodine, Evgenia

AU - Venegas-Yazigi, Diego

PY - 2012/9/7

Y1 - 2012/9/7

N2 - Hydrothermal synthesis was used to obtain four new crystalline lattices derived from the functionalization of the [V12B18O 60H6]n- cluster: Na8(H 3O){[Ni(H2O)5][V12B 18O60H6]}·12.5H2O (1), Na5 (H3O)4{[Ni (H2O) 3(en)][V12B18O60H 6]}·9H2O (2), and Na9(H 3O){Zn0.5[V12B18O60H 6]}·11H2O (3), [Hen][H2en]{[Zn(en) 2]3 [V12B18O60H 6]}·3H2O (4). All four compounds crystallize in the space group C2/c. Compounds (1) (2) and (4) are 0D species, while for (3) there is some degree of covalent connectivity between the anionic units, due to the presence of ZnII cations with partial occupation between them. On the basis of structural data and BVS calculations, these functionalized cluster species present mixed-valence ratios of 11VIV/1VV for (1), (2) and (3) and 9VIV/3VV for compound (4). Compounds (1), (2) and (3) present sodium and hydronium ions in the crystalline lattice, while protonated ethylenediamine is observed in compound (4). These cations balance the negative charge of the corresponding clusters and stabilize the crystalline lattice by electrostatic interactions. In the studied compounds, NiII ions coordinate to the vanadyl oxygen atoms, whereas the ZnII cations coordinate both to the vanadyl oxygen atoms and to the oxygen atoms bonded to boron centres. The electronic spectra in the low energy range are dominated by the IVCT phenomenon, since the functionalization of the cluster [V12B18O60H6]n- by different transition metal ions does not affect the observed absorption bands.

AB - Hydrothermal synthesis was used to obtain four new crystalline lattices derived from the functionalization of the [V12B18O 60H6]n- cluster: Na8(H 3O){[Ni(H2O)5][V12B 18O60H6]}·12.5H2O (1), Na5 (H3O)4{[Ni (H2O) 3(en)][V12B18O60H 6]}·9H2O (2), and Na9(H 3O){Zn0.5[V12B18O60H 6]}·11H2O (3), [Hen][H2en]{[Zn(en) 2]3 [V12B18O60H 6]}·3H2O (4). All four compounds crystallize in the space group C2/c. Compounds (1) (2) and (4) are 0D species, while for (3) there is some degree of covalent connectivity between the anionic units, due to the presence of ZnII cations with partial occupation between them. On the basis of structural data and BVS calculations, these functionalized cluster species present mixed-valence ratios of 11VIV/1VV for (1), (2) and (3) and 9VIV/3VV for compound (4). Compounds (1), (2) and (3) present sodium and hydronium ions in the crystalline lattice, while protonated ethylenediamine is observed in compound (4). These cations balance the negative charge of the corresponding clusters and stabilize the crystalline lattice by electrostatic interactions. In the studied compounds, NiII ions coordinate to the vanadyl oxygen atoms, whereas the ZnII cations coordinate both to the vanadyl oxygen atoms and to the oxygen atoms bonded to boron centres. The electronic spectra in the low energy range are dominated by the IVCT phenomenon, since the functionalization of the cluster [V12B18O60H6]n- by different transition metal ions does not affect the observed absorption bands.

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U2 - 10.1039/c2ce25436k

DO - 10.1039/c2ce25436k

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JO - CrystEngComm

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Hermosilla-Ibáñez P, Car PE, Vega A, Costamagna J, Caruso F, Pivan JY y otros. New structures based on the mixed valence polyoxometalate cluster [V 12B18O60H6]n-. CrystEngComm. 2012 sep 7;14(17):5604-5612. https://doi.org/10.1039/c2ce25436k