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Opening of the Diamondoid Cage upon Ionization Probed by Infrared Spectra of the Amantadine Cation Solvated by Ar, N2, and H2O

George, Martin Andreas Robert; Dopfer, Otto

FG Lasermolekülspektroskopie und Umweltphysik

Radical cations of diamondoids, a fundamental class of very stable cyclic hydrocarbon molecules, play an important role in their functionalization reactions and the chemistry of the interstellar medium. Herein, we characterize the structure, energy, and intermolecular interaction of clusters of the amantadine radical cation (Ama+, 1‐aminoadamantane) with solvent molecules of different interaction strength by infrared photodissociation (IRPD) spectroscopy of mass‐selected Ama+Ln clusters, with L=Ar (n≤3) and L=N2 and H2O (n=1), and dispersion‐corrected density functional theory calculations (B3LYP−D3/cc‐pVTZ). Three isomers of Ama+ generated by electron ionization are identified by the vibrational properties of their rather different NH2 groups. The ligands bind preferentially to the acidic NH2 protons, and the strength of the NH…L ionic H‐bonds are probed by the solvation‐induced red‐shifts in the NH stretch modes. The three Ama+ isomers include the most abundant canonical cage isomer (I) produced by vertical ionization, which is separated by appreciable barriers from two bicyclic distonic iminium ions obtained from cage‐opening (primary radical II) and subsequent 1,2 H‐shift (tertiary radical III), the latter of which is the global minimum on the Ama+ potential energy surface. The effect of solvation on the energetics of the potential energy profile revealed by the calculations is consistent with the observed relative abundance of the three isomers. Comparison to the adamantane cation indicates that substitution of H by the electron‐donating NH2 group substantially lowers the barriers for the isomerization reaction.