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000830302 0247_ $$2doi$$a10.1021/acs.jpcc.7b02138
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000830302 1001_ $$0P:(DE-HGF)0$$aLinnenberg, Oliver$$b0
000830302 245__ $$aMolecular Characteristics of a Mixed-Valence Polyoxovanadate {V IV/V 18 O 42 } in Solution and at the Liquid–Surface Interface
000830302 260__ $$aWashington, DC$$bSoc.$$c2017
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000830302 520__ $$aThe 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.
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000830302 7001_ $$0P:(DE-Juel1)145323$$aMoors, Marco$$b1
000830302 7001_ $$0P:(DE-HGF)0$$aSolé-Daura, Albert$$b2
000830302 7001_ $$0P:(DE-HGF)0$$aLópez, Xavier$$b3
000830302 7001_ $$0P:(DE-Juel1)159254$$aBäumer, Christoph$$b4
000830302 7001_ $$0P:(DE-Juel1)130754$$aKentzinger, Emmanuel$$b5
000830302 7001_ $$0P:(DE-Juel1)130902$$aPyckhout-Hintzen, Wim$$b6
000830302 7001_ $$0P:(DE-Juel1)167441$$aMonakhov, Kirill$$b7$$eCorresponding author$$ufzj
000830302 773__ $$0PERI:(DE-600)2256522-X$$a10.1021/acs.jpcc.7b02138$$gVol. 121, no. 19, p. 10419 - 10429$$n19$$p10419 - 10429$$tThe @journal of physical chemistry <Washington, DC> / C$$v121$$x1932-7455$$y2017
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