Hydrogen bonding interaction plays an essential role in the early phases of molecular recognition and colorimetric sensing of various anions in aprotic media. In this work, the host-guest interaction between fac-[Re(CO)(3)Cl(L)] with L = 4-([2,2'-bipyridin]-4-yl)phenol and fluoride ions is investigated for the hydrogen bond dynamics and the changing local coordination environment. The stoichiometric studies using H-1 NMR and ESI-MS spectroscopies have shown that proton transfer in the H-bonded phenol-fluoride complex activates the dissociation of the CO ligand in the Re(I) center. The phenol-to-phenolate conversion during formation of HF2- ion induces nucleophilic lability of the CO ligand which is probed by intraligand charge transfer (ILCT) and ligand-to-metal charge transfer (LMCT) transitions in transient absorption spectroscopy. After photoexcitation, phenol-phenoxide conversion rapidly equilibrates in 280 fs time scale and the ensuing excited state [ReII(bpy(center dot-)-phenolate(-))(CO)(3)Cl]* undergoes CO dissociation in the ultrafast time scale of similar to 3 ps. A concerted mechanism of hydrogen cleavage and coordination change is established in anion sensing studies of the rhenium complex.