Isomer-selective detection of microsolvated oxonium and carbenium ions of protonated phenol: infrared spectra of C6H7O+-Ln clusters (L=Ar/N2, n

Abstract

Infrared photodissociation (IRPD) spectra of clusters composed of protonated phenol (C(6)H(7)O(+)) and several ligands L are recorded in the O-H and C-H stretch ranges using a tandem mass spectrometer coupled to a cluster ion source. The C(6)H(7)O(+)-L(n) complexes (L=Ar/N(2), n=1-6) are generated by chemical ionization of a supersonic expansion. The IRPD spectra of mass selected C(6)H(7)O(+)-L(n) clusters obtained in various C(6)H(7)O(+)-L(m) fragment channels (m<n) display the unambiguous fingerprints of at least two different C(6)H(7)O(+) nucleation centers: the oxonium ion (5) and the carbenium ion(s) corresponding to protonation of phenol in ortho and/or para position (1/3). These two classes of C(6)H(7)O(+)-L(n) isomers show very different fragmentation behavior upon IR excitation, facilitating the assignment of the observed vibrational transitions. The vibrational frequency shifts as a function of cluster size reveal that the microsolvation of 1/3 and 5 in Ar and N(2) begins with the formation of intermolecular hydrogen bond(s) to the acidic OH group(s) and proceeds by the formation of intermolecular pi-bonds to the respective six-membered rings. The analysis of photofragmentation branching ratios yields estimated ligand binding energies of the intermolecular OH- and pi-bonds for solvation of the different C(6)H(7)O(+) isomers. The effects of microsolvation on the properties of 1/3 as reactive intermediates in electrophilic aromatic substitution reactions are discussed. Comparison of clusters of protonated phenol with those of neutral phenol reveals the drastic protonation-induced changes in the topology of the intermolecular potential of aromatic molecules interacting with a nonpolar solvent. Moreover, the results show that the IRPD process can be used to selectively generate a spectroscopically clean ion beam of either 1/3 or 5 with some control over their internal energies.