Author, as appears in the article.: Linnenberg O; Moors M; Solé-Daura A; López X; Bäumer C; Kentzinger E; Pyckhout-Hintzen W; Monakhov K
Department: Química Física i Inorgànica
URV's Author/s: López Fernández, Javier
Abstract: © 2017 American Chemical Society. 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 [VIV10VV8O42(I)]5- charged balanced by Et4N+ 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 (NEt4)5[V18O42(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 H2O molecules between POVs that are surrounded by the Et4N+ 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 Et4N+ ions and a small number of H2O 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 round-shaped 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.
Thematic Areas: Surfaces, coatings and films Química Physical and theoretical chemistry Nanoscience and nanotechnology Nanoscience & nanotechnology Medicina ii Medicina i Materials science, multidisciplinary Materiais Interdisciplinar General energy Farmacia Ensino Engenharias iv Engenharias iii Engenharias ii Engenharias i Energy (miscellaneous) Energy (all) Electronic, optical and magnetic materials Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Ciências ambientais Ciências agrárias i Chemistry, physical Biotecnología Biodiversidade Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 19327447
Author's mail: javier.lopez@urv.cat
Author identifier: 0000-0003-0322-6796
Record's date: 2024-09-07
Papper version: info:eu-repo/semantics/acceptedVersion
Link to the original source: https://pubs.acs.org/doi/10.1021/acs.jpcc.7b02138
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Journal Of Physical Chemistry c. 121 (19): 10419-10429
APA: Linnenberg O; Moors M; Solé-Daura A; López X; Bäumer C; Kentzinger E; Pyckhout-Hintzen W; Monakhov K (2017). Molecular Characteristics of a Mixed-Valence Polyoxovanadate {VIV/V18O42} in Solution and at the Liquid-Surface Interface. Journal Of Physical Chemistry c, 121(19), 10419-10429. DOI: 10.1021/acs.jpcc.7b02138
Article's DOI: 10.1021/acs.jpcc.7b02138
Entity: Universitat Rovira i Virgili
Journal publication year: 2017
Publication Type: Journal Publications
Repositori URV