Molecular Characteristics of a Mixed-Valence Polyoxovanadate {VIV/V18O42} in Solution and at the Liquid-Surface Interface

Oliver Linnenberg, Marco Moors, Albert Solé-Daura, Xavier López, Christoph Bäumer, Emmanuel Kentzinger, Wim Pyckhout-Hintzen, Kirill Yu Monakhov*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

20 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)10419-10429
Number of pages11
JournalJournal of physical chemistry C
Volume121
Issue number19
DOIs
Publication statusPublished - 18 May 2017
Externally publishedYes

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