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@ARTICLE{Han:58667,
      author       = {Han, B. and Li, Z. and Wandlowski, Th. and Blaszcyk, A. and
                      Mayor, M.},
      title        = {{P}otential-induced redox {S}witching in {V}iologen
                      {S}elf-assembled {M}onolayers - {A}n {ATR}-{SEIRAS}
                      {A}pproach},
      journal      = {The journal of physical chemistry / C},
      volume       = {111},
      issn         = {1932-7447},
      address      = {Washington, DC},
      publisher    = {Soc.},
      reportid     = {PreJuSER-58667},
      pages        = {13855 - 13863},
      year         = {2007},
      note         = {Record converted from VDB: 12.11.2012},
      abstract     = {Monolayers of viologens
                      (N-alkyl-N'-(n-thioalkyl)-4,4'-bipyridinium bromide, n = 6,
                      8, 10) have been self-assembled from ethanolic solution onto
                      gold substrates. Their structure and redox functionality
                      were studied by cyclic voltammetry and in situ ATR-SEIRAS.
                      Voltammetric experiments revealed that the first redox
                      process, V2+ <-> V center dot+, is reversible, whereas the
                      second redox process, V center dot+ <-> V-0, is quasi
                      reversible. The V2+ adlayer exhibits a sandwich-like
                      structure. Van der Waals interactions between the alkyl
                      chains lead to two well-ordered hydrophobic layers, with the
                      redox-active bipyridinium unit enclosed in between. The
                      alkyl chains are aligned in an all-trans configuration in a
                      tilted orientation with respect to the surface normal and
                      exhibit a slight conformational disorder. The long axis of
                      the central bipyridinium rings is also tilted. The alignment
                      of V2+ is stabilized by interplanar pi-pi stacking and
                      electrostatic coulomb interactions. Both monomers and dimers
                      of V center dot+ coexist in the V center dot+ adlayer. The
                      molecular alignment of the V center dot+ adlayer is
                      stabilized by the strong vibronic coupling within the dimers
                      and the pi-pi stacking between the monomers. Increasing
                      length of the alkyl chain results in more tilted
                      bipyridinium units, and favors both the dimerization and the
                      alignment of V center dot+ within the SAMs. The complex
                      reaction, V2+ - V center dot+, is described as electron
                      transport from the electrode to the V2+ moiety followed by
                      the dimerization of V center dot+, the delocalization of the
                      radical electrons, and the migration of coadsorbed ClO4-
                      anions.},
      keywords     = {J (WoSType)},
      cin          = {IBN-3 / CNI / JARA-FIT},
      ddc          = {540},
      cid          = {I:(DE-Juel1)VDB801 / I:(DE-Juel1)VDB381 /
                      $I:(DE-82)080009_20140620$},
      pnm          = {Grundlagen für zukünftige Informationstechnologien},
      pid          = {G:(DE-Juel1)FUEK412},
      shelfmark    = {Chemistry, Physical / Nanoscience $\&$ Nanotechnology /
                      Materials Science, Multidisciplinary},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000249501800032},
      doi          = {10.1021/jp073208g},
      url          = {https://juser.fz-juelich.de/record/58667},
}