Ultraviolet-visible spectroelectrochemistry of chemisorbed molecular layers on optically transparent carbon electrodes.

Pyrolysis of diluted commercial photoresist spun onto quartz slides yields optically transparent graphitic films. Transparent carbon electrodes approximately 6 nm thick can be reproducibly prepared, with a maximum absorbance in the ultraviolet-visible (UV-vis) range of 0.25 at 270 nm. These electrodes are sufficiently conductive for electrochemistry, enabling modification of the surface via diazonium ion reduction and spectroelectrochemistry. Good quality ultraviolet-visible absorption spectra of covalently bonded molecular layers of nitroazobenzene, nitrobiphenyl, and azobenzene, with thicknesses of 1.4-4 nm, were obtained after subtracting the spectrum of the unmodified substrate. The spectra of all three molecules immobilized on the carbon surface showed red shifts of the absorption maxima relative to a solution of free molecules, indicating substantial electronic interactions between chemisorbed molecules and the Pi system of the substrate and/or intermolecular coupling. Spectroelectrochemical measurements show that reduction of free and chemisorbed molecules produce new absorption features in the 500-800 nm range; these spectral changes are partially reversible upon repeated potential cycling. Finally, density functional calculations correlate the new bands to the formation of anion radical or "methide" species that have more extensive electron delocalization than the parent molecules. The results from this work are useful for linking structural transformations in molecular layers "buried" under conductive top contacts in a type of molecular junction to changes in the electronic properties of the junction.