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@ARTICLE{Linnenberg:830302,
      author       = {Linnenberg, Oliver and Moors, Marco and Solé-Daura, Albert
                      and López, Xavier and Bäumer, Christoph and Kentzinger,
                      Emmanuel and Pyckhout-Hintzen, Wim and Monakhov, Kirill},
      title        = {{M}olecular {C}haracteristics of a {M}ixed-{V}alence
                      {P}olyoxovanadate {{V} {IV}/{V} 18 {O} 42 } in {S}olution
                      and at the {L}iquid–{S}urface {I}nterface},
      journal      = {The journal of physical chemistry / C},
      volume       = {121},
      number       = {19},
      issn         = {1932-7455},
      address      = {Washington, DC},
      publisher    = {Soc.},
      reportid     = {FZJ-2017-03870},
      pages        = {10419 - 10429},
      year         = {2017},
      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.},
      cin          = {JCNS-2 / PGI-4 / JARA-FIT / PGI-7 / Neutronenstreuung ;
                      JCNS-1},
      ddc          = {540},
      cid          = {I:(DE-Juel1)JCNS-2-20110106 / I:(DE-Juel1)PGI-4-20110106 /
                      $I:(DE-82)080009_20140620$ / I:(DE-Juel1)PGI-7-20110106 /
                      I:(DE-Juel1)JCNS-1-20110106},
      pnm          = {144 - Controlling Collective States (POF3-144) / 524 -
                      Controlling Collective States (POF3-524) / 6212 - Quantum
                      Condensed Matter: Magnetism, Superconductivity (POF3-621) /
                      6213 - Materials and Processes for Energy and Transport
                      Technologies (POF3-621)},
      pid          = {G:(DE-HGF)POF3-144 / G:(DE-HGF)POF3-524 /
                      G:(DE-HGF)POF3-6212 / G:(DE-HGF)POF3-6213},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000402024200020},
      doi          = {10.1021/acs.jpcc.7b02138},
      url          = {https://juser.fz-juelich.de/record/830302},
}