2006
DOI: 10.1039/b506623a
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Two-dimensional assembly and local redox-activity of molecular hybrid structures in an electrochemical environment

Abstract: The self-assembly and redox-properties of two viologen derivatives, N-hexyl-N 0 -(6-thiohexyl)-4,4 0 -bipyridinium bromide (HS-6V6-H) and N,N 0 -bis(6-thiohexyl)-4,4 0 -bipyridinium bromide (HS-6V6-SH), immobilized on Au(111)-(1 Â 1) macro-electrodes were investigated by cyclic voltammetry, surface enhanced infrared spectroscopy (SEIRAS) and in situ scanning tunneling microscopy (STM). Depending on the assembly conditions one could distinguish three different types of adlayers for both viologens: a low coverag… Show more

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Cited by 142 publications
(259 citation statements)
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“…In the electrochemical scanning tunneling spectroscopy configuration (i.e., STM tip not chemically attached to the molecule) there is now a collection of examples displaying a clear maximum in their tunneling current (I tunneling ) vs electrochemical potential relations. 13,15,[23][24][25][26][27]29,39 These have been well-modeled in terms of the KU relationship for two-step electron/hole transfer through the redox center in the STM−substrate gap. The situation is far from clear for measurements made in the in situ electrochemically gated BJ configuration (i.e., when the electrochemically active bridge molecule is chemically attached at one end to the STM tip and at the other end to the substrate).…”
Section: ■ Introductionmentioning
confidence: 99%
“…In the electrochemical scanning tunneling spectroscopy configuration (i.e., STM tip not chemically attached to the molecule) there is now a collection of examples displaying a clear maximum in their tunneling current (I tunneling ) vs electrochemical potential relations. 13,15,[23][24][25][26][27]29,39 These have been well-modeled in terms of the KU relationship for two-step electron/hole transfer through the redox center in the STM−substrate gap. The situation is far from clear for measurements made in the in situ electrochemically gated BJ configuration (i.e., when the electrochemically active bridge molecule is chemically attached at one end to the STM tip and at the other end to the substrate).…”
Section: ■ Introductionmentioning
confidence: 99%
“…Conductance switching in molecular junctions has been demonstrated previously using various means including light, 1, 2 bias pulses, 3 electrostatic-, 4,5 and electrochemical gating. 6,7 The concept of "electrochemical gating" which provides the opportunity to overcome the technical challenges of incorporating a gate electrode in a solid-state molecular device, has been employed in electrochemically active molecular systems, including viologens, [8][9][10] oligoaniline, 11 ferrocene, [12][13][14] transition metal complexes, 7,15,16 perylenebisimides, [17][18][19] redox-active proteins, 20,21 quinones 22,23 and tetrathiafulvalene, 24 as well as redox-inactive molecules. 25 In the case of redox-inactive molecules, or more generally when the electrode potential does not overlap with the molecule's redox potential, the effect of the gate is simply to shift the molecular levels up or down in energy relative to the Fermi level.…”
mentioning
confidence: 99%
“…20 This expectation has been supported by a number of recent experimental studies. [31][32][33][34][35][36][37][38] Not only the maximum itself has been clearly observed but the dependence of maximum current and the position of the maximum on the bias voltage has also been studied 32,33 and analyzed. 32 Closer examination of Tao's data shows that the current maximum for this system is also close to the equilibrium potential.…”
Section: Introductionmentioning
confidence: 99%