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The effect of the distance between a β-cyclodextrin (βCD) host core and a conductive substrate on the electron-transfer rate of complexed guests as well as of free-diffusing electrochemically active probes has been studied. First we have evaluated a set of short-tethered βCD adsorbates bearing different anchoring groups in order to get a reliable platform for the study of short-distance electron transfer. An electrochemically active trivalent guest was immobilized on these host monolayers in a selective and reversible manner, providing information about the packing density. Iodine- and nitrile-functionalized βCD monolayers gave coverages close to maximum packing. Electron transfer in the presence of Fe(CN)6 3-/4- studied by impedance spectroscopy revealed that the electron transfer of the diffusing probe was 3 orders of magnitude faster than when the βCD cores were separated from the surface by undecyl chains. When an electrochemically active guest was immobilized on the surface, electron-transfer rate measurements by cyclic voltammetry and capacitance spectroscopy showed differences of up to a factor of 8 for different βCD monolayers. These results suggest that increasing the distance between the βCD core and the underlying conductive substrate leads to a diminishing of the electron-transfer rate.

We designed multivalent β-cyclodextrin-based adsorbates bearing different anchoring groups aiming to yield stable monolayers with improved packing and close contact of the cavity to the gold surface. Toward this end the primary rim of the β-cyclodextrin was decorated with several functional groups, namely iodide, nitrile, amine, isothiocyanate, methyl sulfide, and isocyanide. Monolayers formed by these adsorbates were characterized by contact angle measurements, surface plasmon resonance spectroscopy, polarization modulation infrared reflection adsorption spectroscopy, X-ray photoelectron spectroscopy, and electrochemistry. The nature of the anchoring group influenced the adsorption kinetics, thickness, layer stability, number of anchoring groups bounded to the surface, and packing in the resulting monolayers. Therefore, chemical manipulation of multivalent adsorbates can be used to modify the properties of their monolayers.