Microhydration of the adamantane cation: intracluster proton transfer to solvent in [Ad(H₂O)]⁺ for n ≥ 3

Radical cations of diamondoids are important intermediates in their functionalization reactions in polar solvents. To explore the role of the solvent at the molecular level, we characterize herein microhydrated radical cation clusters of the parent molecule of the diamondoid family, adamantane (C₁₀H₁₆, Ad), by infrared photodissociation (IRPD) spectroscopy of mass-selected [Ad(H₂O)]⁺ clusters. IRPD spectra of the cation ground electronic state recorded in the CH/OH stretch and fingerprint ranges reveal the first steps of this fundamental H-substitution reaction at the molecular level. Analysis of size-dependent frequency shifts with dispersion-corrected density functional theory calculations (B3LYP-D3/cc-pVTZ) provides detailed information about the acidity of the proton of Ad⁺ as a function of the degree of hydration, the structure of the hydration shell, and the strengths of the CH⋯O and OH⋯O hydrogen bonds (H-bonds) of the hydration network. For n = 1, H₂O strongly activates the acidic C-H bond of Ad⁺ by acting as a proton acceptor in a strong CH⋯O ionic H-bond with cation-dipole configuration. For n = 2, the proton is almost equally shared between the adamantyl radical (C₁₀H₁₅, Ady) and the (H₂O)₂ dimer in a strong C⋯H⋯O ionic H-bond. For n ≥ 3, the proton is completely transferred to the H-bonded hydration network. The threshold for this size-dependent intracluster proton transfer to solvent is consistent with the proton affinities of Ady and (H₂O) and confirmed by collision-induced dissociation experiments. Comparison with other related microhydrated cations reveals that the acidity of the CH proton of Ad⁺ is in the range of strongly acidic phenol⁺ but lower than for cationic linear alkanes such as pentane⁺. Significantly, the presented IRPD spectra of microhydrated Ad⁺ provide the first spectroscopic molecular-level insight of the chemical reactivity and reaction mechanism of the important class of transient diamondoid radical cations in aqueous solution.