Rapid Electron Tunneling Through Oligophenylenevinylene Bridges

Abstract

We measured rate constants of thermal, interfacial electron transfer through oligophenylenevinylene bridges between a gold electrode and a tethered redox species in contact with an aqueous electrolyte using the indirect laser-induced temperature jump technique. Analysis of the distance dependence indicates that, unlike other bridges studied to date, the rate constants are not limited by electronic coupling for bridges up to 28 angstroms long. The energy levels of the bridges relative to those of the redox species rule out hopping through the bridge. We conclude that, out to 28 angstroms, the transfer is limited by structural reorganization and that electron tunneling occurs in less than 20 picoseconds, suggesting that oligophenylenevinylene bridges could be useful for wiring molecular electronic elements.

Rate of Interfacial Electron Transfer through the 1,2,3-Triazole Linkage

“…These results are expected based on previous work on mixed monolayers formed by coadsorption of diluent thiols with thiols terminated by redox species. 3,4,6,9,12,15,18 One sees from Table 1 that the rate of electron transfer to the clickcoupled redox couples can readily be scaled by over 4 orders of magnitude by modifying the nature of the azide-terminated mixed monolayer.…”

“…[2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] One of the major limits to the routine use of this method is the difficulty of forming the desired assemblies of electrode, monolayer, and redox species. Typical assembly strategies rely on appending a spacer or electron-transfer "bridge" terminated with a thiol group to the redox species of interest and then coadsorbing this molecule with a more plentiful unmodified or "diluent" thiol.…”

When Voltammetry Reaches Nanoseconds

“…Virtually any functional group can be anchored at the other end of the molecule. Thus, this self-assembly technique provides a simple way for interrogating the properties of the chain linker or the redox active group (4,(18)(19)(20)(21). With this approach, electron transfer through alkane chains can thus be extensively studied.…”

First-principles investigation of electron-induced cross-linking of aromatic self-assembled monolayers on Au(111)

“…A large part of the interest has focussed on aromatic moieties as an alternative of alkane-based spacers. [6][7][8][9][10][11] Aromatic SAMs differ significantly from the aliphatic ones in geometry and intermolecular interactions, so they show different charge-transfer properties [12][13][14] and different behaviour during electron irradiation. 15,16 Here, we are interested in SAMs containing spacers formed by biphenyl (BP) groups, and, in particular, in the modifications of the structures of these films after the dehydrogenization process induced by electron irradiation.…”