Spectral Signatures of Oxidation States in a Manganese-Oxo Cubane Water Oxidation Catalyst.
Chemistry
; 27(68): 17078-17086, 2021 Dec 06.
Article
em En
| MEDLINE
| ID: mdl-34523763
ABSTRACT
We report IR and UV/Vis spectroscopic signatures that allow discriminating between the oxidation states of the manganese-based water oxidation catalyst [(Mn4 O4 )(V4 O13 )(OAc)3 ]3- . Simulated IR spectra show that V=O stretching vibrations in the 900-1000â
cm-1 region shift consistently by about 20â
cm-1 per oxidation equivalent. Multiple bands in the 1450-1550â
cm-1 region also change systematically upon oxidation/reduction. The computed UV/Vis spectra predict that the spectral range above 350â
nm is characteristic of the managanese-oxo cubane oxidation state, whereas transitions at higher energy are due to the vanadate ligand. The presence of absorption signals above 680â
nm is indicative of the presence of MnIII atoms. Spectroelectrochemical measurements of the oxidation from [Mn 2 III Mn 2 IV ] to [Mn 4 IV ] showed that the change in oxidation state can indeed be tracked by both IR and UV/Vis spectroscopy.
Palavras-chave
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Água
/
Manganês
Tipo de estudo:
Prognostic_studies
País/Região como assunto:
Cuba
Idioma:
En
Revista:
Chemistry
Assunto da revista:
QUIMICA
Ano de publicação:
2021
Tipo de documento:
Article
País de afiliação:
Áustria