Autor según el artículo: Laurans M; Mattera M; Salles R; K'Bidi L; Gouzerh P; Renaudineau S; Volatron F; Guillemot G; Blanchard S; Izzet G; Solé-Daura A; Poblet JM; Proust A
Departamento: Química Física i Inorgànica
Autor/es de la URV: Poblet Rius, Josep Maria / Solé Daura, Albert
Palabras clave: Molecular-orbital methods vibrational investigations redox potentials post-functionalization metal-oxide clusters magnetic-properties heteropoly blues electron delocalization charge-separation ab-initio calculation
Resumen: The mixed molybdenum/tungsten Keggin-type polyoxometalate (POM) hybrid (TBA)4[PW9Mo2O39{Sn(C6H4I)}] (TBA = tert-butylammonium) has been prepared by the reaction between [α-PW9Mo2O39]7- and [Cl3Sn(C6H4I)] in dried acetonitrile, in the presence of tetra-n-butylammonium bromide. A further coupling reaction affords the ferrocenyl derivative (TBA)4[PW9Mo2O39{Sn(C6H4)C≡C(C6H4)Fc}]. The POM hybrids have been thoroughly characterized by NMR and IR spectroscopies. Electrochemical analysis confirms their ease of reduction compared to the all-W analogue, albeit with a second reduction process occurring at a lower potential than in the all-Mo species. It is noteworthy that the second reduction is accompanied by an unusual red shift of the electronic absorption spectrum. Whereas there is no doubt that the first reduction deals with Mo, the location of the second electron in the bireduced species, on the second Mo or on W, has thus been the subject of a cross-investigation by spectroelectrochemistry, electron spin resonance, and theoretical calculations. Finally, it came out that the second reduction is also Mo-centered with two unpaired and antiferromagnetically coupled extra electrons.
Áreas temáticas: Química Physical and theoretical chemistry Medicina i Materiais Interdisciplinar Inorganic chemistry General medicine Farmacia Engenharias iii Engenharias ii Engenharias i Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências agrárias i Chemistry, inorganic & nuclear Chemistry (miscellaneous) Biotecnología Astronomia / física
Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
Direcció de correo del autor: josepmaria.poblet@urv.cat
Identificador del autor: 0000-0002-4533-0623
Fecha de alta del registro: 2024-09-07
Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
Referencia al articulo segun fuente origial: Inorganic Chemistry. 61 (20): 7700-7709
Referencia de l'ítem segons les normes APA: Laurans M; Mattera M; Salles R; K'Bidi L; Gouzerh P; Renaudineau S; Volatron F; Guillemot G; Blanchard S; Izzet G; Solé-Daura A; Poblet JM; Proust A (2022). When Identification of the Reduction Sites in Mixed Molybdenum/Tungsten Keggin-Type Polyoxometalate Hybrids Turns Out Tricky. Inorganic Chemistry, 61(20), 7700-7709. DOI: 10.1021/acs.inorgchem.2c00866
DOI del artículo: 10.1021/acs.inorgchem.2c00866
Entidad: Universitat Rovira i Virgili
Año de publicación de la revista: 2022
Tipo de publicación: Journal Publications