Infrared (IR) spectra of phenol-Ar/Kr in high-n Rydberg states converging to the cation ground state were measured by autoionization detected IR (ADIR) spectroscopy. Although the clusters were excited via the S-1 state of the pi-bound structures, the ADIR spectra exhibit free and hydrogen-bonded OH stretching vibrations (V-OH). Thus, similar to direct photoionization, excitation into high-n Rydberg states causes the pi-H site switching of the rare gas ligand from the aromatic ring to the OH group. This result demonstrates that the Rydberg electron is insensitive to the dynamics in the ion core. (C) 2011 Published by Elsevier B.V.