Guest molecules can be partially removed from the host cavity by immersing the functionalised electrodes in dimethyl sulfoxide for 90 min (Figure ), which allows for the exchange of different guest molecules. Scan rate dependence experiments revealed a linear relationship of the peak current with respect to the scan rate, as expected for surface-bound molecules (Figure ). To assess the stability of the host-guest binding between PA [6] and compounds 1, 2 and 3, NMR titration studies were conducted in MeOD. High binding constants were observed for all three guest molecules in solution. Guests 1 and 2 exhibited K11 values of 2891 ± 391 M -1 and 2260 ± 362 M -1 , respectively (Figures , Tables ). Notably, extreme peak broadening of the hostspecific signals was induced by guest 3, attributed to an enhanced t2 relaxation time caused by restricted molecular movement of the host molecules resulting from strong binding (Figure , Table ). Hence, the shift change in the methylene signal could not be precisely monitored, leading to a binding constant with a relatively large uncertainty (K11 = 16492 ± 11860 M -1 ). To confirm this assumption on the enhancement of the t2 relaxation time, temperature-dependent studies were conducted. Indeed, upon heating of the sample (308-323 K), signal sharpness was regained due to increased molecular movement (Figure ). Cyclic voltammetry experiments were carried out on the three host-guest complexes to gain insight into their electrochemical characteristics (Figure ). Given that the first electrocatalytic reaction under investigation was the oxidation of benzyl alcohol to benzaldehyde, a reaction that proceeds efficiently under acidic conditions, the experiments were conducted in aqueous electrolyte at pH 2.4. The three catalysts showed the expected redox waves for the Ru II /Ru III oxidation at 0.7, 0.8 and 0.75 V vs. NHE for guests 1 (red), 2 (blue) and 3 (green), respectively. A less pronounced wave was present for the Ru III /Ru IV oxidation between 1.35-1.45 V vs. NHE for all Ru complexes. Upon the addition of benzyl alcohol substrate (10 mM), catalytic onset is observed at 1.3 V vs. NHE for 1 and 3, roughly aligning with the aforementioned Ru III /Ru IV oxidative wave (Figure ). A larger overpotential was required to initiate alcohol oxidation with complex 2, where catalytic onset starts at 1.45 V vs. NHE (Figure ). Based on these results, chronoamperometry (CA) experiments were conducted to evaluate the catalytic activity of the Ru catalysts. Electrocatalysis was performed at 1.7 V vs. NHE for a duration of 2 h (Figure ). Product formation and faradaic efficiency (FE) were quantified by 1 H NMR spectroscopy of the resultant reaction mixtures (Figure ). The outcomes of these catalytic assays are summarised in Table . Notably, the faradaic efficiency of all host-guest complexes remained consistently high, ranging between 88-92%, indicating minimal background water oxidation. This observation was further confirmed when chronoamperometry was performed in the absence of the substrate (Table ). Turnover numbers (TON) were in the low hundreds, with the best-performing catalyst (1) achieving 432 ± 36 for the initial absorption. We note that samples prepared by physisorption of the Ru complexes on mITO electrodes (bare mITO, without PA [6]) did not yield significant charge accumulation or product formation (Table ). Throughout the CA experiments, a gradual degradation of the catalyst became evident, manifested by the diminishing current densities over time. Nonetheless, PA [6] remained stably anchored onto the mITO electrode. This was evidenced by reabsorption of the catalyst upon immersion of the used electrodes into a fresh solution of the Ru complexes (Table ).