Formation of the HGC on the Au surfaces was visualized by the appearance of an intense Raman fingerprint of the guest between 1000 and 1600 cm -1 compared to the moderately strong ν(C-H) band of 1 at 2900 cm -1 (cyclodextrins are very weak Raman scatterers). Desorption of the majority of guest was achieved by soaking and sonication of the sample in a concentrated β-CD solution (indicated by the strong decrease in the guest/host Raman band intensity ratio). Re-adsorption of the guest was observed after re-soaking the desorbed sample in a solution of 3. In a separate experiment, we also showed that guest 4 (Pt complex) can be exchanged for a second guest 2 by initial desorption of 4 using concentrated β-CD solution and subsequent incubation in a solution of guest 2 (Figure ). The exchange was enabled by the release of guest 4 from the surface-bound host cavities during the desorption step and cannot be explained with stronger binding of guest 2 compared to guest 4, as the reverse exchange (2 for 4) is also feasible (Figure ). Interestingly, complete loss of guest signal after the desorption treatment was never observed, which again hints towards the unexpectedly strong interaction between the guest and the 1-functionalized gold. Raman and TERS measurements of guest 2 revealed a red-shift of the guest's optical absorption maximum upon host-guest binding on the gold surface, which illustrates the shrinking of the HOMO-LUMO gap predicted by the DFT calculations, providing further evidence for the strong coupling between the gold substrate and the guest (Figure ). Direct observation of 1 and the HGCs on Au(111) was attempted by STM, however a clear image could not be obtained despite significant efforts (Figure ).