Surface-Immobilized Pyridine-Functionalized γ-Cyclodextrin:  Alkanethiol Co-adsorption-Induced Reorientation

Monolayers of di-6A,6B-deoxy-6-(4-pyridylmethyl)amino-γ-cyclodextrin (γ-CD-(py)2) have been formed on polycrystalline platinum electrodes and investigated using electrochemical and surface-enhanced Raman spectroscopy (SERS). The behavior of self-assembled monolayers of (γ-CD-(py)2) alone, (γ-CD-(py)2) backfilled with 1-nonanethiol, and 1-nonanethiol are reported. The potential dependence of the capacitance indicates that the film capacitance is higher for the backfilled CD layers than for 1-nonanethiol layers, most likely due to ion flux through the CD cavity. SERS spectra of the backfilled layer exhibit features associated with both pyridine-functionalized CD and alkane moieties. Investigations using [Fe(CN)6]4- as a solution-phase probe indicate that the backfilled CD−alkane thiol layer exhibits enhanced blocking properties compared to γ-CD-(py)2 films alone. Complete blocking was achieved by a combination of backfilling and insertion of a high-affinity guest 1-adamantylamine into the cavity. Significantly, an electroactive guest with high affinity for γ-CD, [Co(biptpy)2]2+, does not exhibit a redox response at the γ-CD-(py)2 layer but molecular recognition is turned on by backfilling the CD layer with 1-nonanethiol molecules. This switching on of the electrochemical activity suggests that the CD hosts are initially inaccessible but reorientate upon backfilling, exposing the CD opening to solution and permitting a supramolecular host−guest complex to form. The binding of [Co(biptpy)2]2+ to γ-CD in the backfilled monolayer depends on the bulk concentration of guest and is modeled by the Langmuir isotherm, yielding an association constant for the Co2+ state of 1.45 ± 0.46 × 105 M-1 and a limiting surface coverage 1.49 ± 0.25 × 10-11 mol cm-2. The surface coverage of the divalent state is higher than the trivalent state, reflecting the dynamic nature of the inclusion.