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000058667 0247_ $$2DOI$$a10.1021/jp073208g
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000058667 084__ $$2WoS$$aChemistry, Physical
000058667 084__ $$2WoS$$aNanoscience & Nanotechnology
000058667 084__ $$2WoS$$aMaterials Science, Multidisciplinary
000058667 1001_ $$0P:(DE-Juel1)VDB35518$$aHan, B.$$b0$$uFZJ
000058667 245__ $$aPotential-induced redox Switching in Viologen Self-assembled Monolayers - An ATR-SEIRAS Approach
000058667 260__ $$aWashington, DC$$bSoc.$$c2007
000058667 300__ $$a13855 - 13863
000058667 3367_ $$0PUB:(DE-HGF)16$$2PUB:(DE-HGF)$$aJournal Article
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000058667 440_0 $$016841$$aJournal of Physical Chemistry C$$v111$$x1932-7447
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000058667 520__ $$aMonolayers of viologens (N-alkyl-N'-(n-thioalkyl)-4,4'-bipyridinium bromide, n = 6, 8, 10) have been self-assembled from ethanolic solution onto gold substrates. Their structure and redox functionality were studied by cyclic voltammetry and in situ ATR-SEIRAS. Voltammetric experiments revealed that the first redox process, V2+ <-> V center dot+, is reversible, whereas the second redox process, V center dot+ <-> V-0, is quasi reversible. The V2+ adlayer exhibits a sandwich-like structure. Van der Waals interactions between the alkyl chains lead to two well-ordered hydrophobic layers, with the redox-active bipyridinium unit enclosed in between. The alkyl chains are aligned in an all-trans configuration in a tilted orientation with respect to the surface normal and exhibit a slight conformational disorder. The long axis of the central bipyridinium rings is also tilted. The alignment of V2+ is stabilized by interplanar pi-pi stacking and electrostatic coulomb interactions. Both monomers and dimers of V center dot+ coexist in the V center dot+ adlayer. The molecular alignment of the V center dot+ adlayer is stabilized by the strong vibronic coupling within the dimers and the pi-pi stacking between the monomers. Increasing length of the alkyl chain results in more tilted bipyridinium units, and favors both the dimerization and the alignment of V center dot+ within the SAMs. The complex reaction, V2+ - V center dot+, is described as electron transport from the electrode to the V2+ moiety followed by the dimerization of V center dot+, the delocalization of the radical electrons, and the migration of coadsorbed ClO4- anions.
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000058667 7001_ $$0P:(DE-Juel1)VDB2436$$aLi, Z.$$b1$$uFZJ
000058667 7001_ $$0P:(DE-Juel1)VDB9859$$aWandlowski, Th.$$b2$$uFZJ
000058667 7001_ $$0P:(DE-HGF)0$$aBlaszcyk, A.$$b3
000058667 7001_ $$0P:(DE-HGF)0$$aMayor, M.$$b4
000058667 773__ $$0PERI:(DE-600)2256522-X$$a10.1021/jp073208g$$gVol. 111, p. 13855 - 13863$$p13855 - 13863$$q111<13855 - 13863$$tThe @journal of physical chemistry <Washington, DC> / C$$v111$$x1932-7447$$y2007
000058667 8567_ $$uhttp://dx.doi.org/10.1021/jp073208g
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000058667 9201_ $$0I:(DE-Juel1)VDB801$$d31.12.2010$$gIBN$$kIBN-3$$lGrenz- und Oberflächen$$x0
000058667 9201_ $$0I:(DE-Juel1)VDB381$$d14.09.2008$$gCNI$$kCNI$$lCenter of Nanoelectronic Systems for Information Technology$$x1$$z381
000058667 9201_ $$0I:(DE-82)080009_20140620$$gJARA$$kJARA-FIT$$lJülich-Aachen Research Alliance - Fundamentals of Future Information Technology$$x2
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