Molecular Structure, Vibrational Spectra, Quantum Chemical Calculations and Photochemistry of Picolinamide and Isonicotinamide Isolated in Cryogenic Inert Matrices and in The Neat Low Temperature Solid Phases

A. BORBA, A. GÓMEZ-ZAVAGLIA AND R. FAUSTO

JOURNAL OF PHYSICAL CHEMISTRY A

American Chemical Society

Lugar: 1100 Seventeenth Street, NW Suite 507 Washington, DC 20036-4632; Año: 2008 vol. 112 p. 45 - 57

1089-5639

Picolinamide (PA) and isonicotinamide (INA), two structural isomers of pyridinecarboxamide, have been investigated by matrix isolation and low-temperature solid-state infrared spectroscopy, combined with UV (lambda > 235 nm) photoexcitation and density functional theory and ab initio (MP2) theoretical studies. In consonance with the theoretical data, both PA and INA were found to exist in a single conformation in cryogenic rare gas matrixes. Comparison between the experimental spectra of the matrix-isolated compounds with those theoretically predicted allowed for full assignment of the experimental spectra. In situ UV (lambda > 235 nm) irradiation of the matrixes showed that only PA reacts, with production of isocyanic acid and pyridine, the first photoproduct further reacting to yield CO + NH and cyanic acid. The different photochemical behavior of the two compounds was explained taking into consideration their different structures. The infrared spectra of (i) the low-temperature glassy state resulting from fast deposition of vapors of the compounds onto a substrate cooled to 10 K, (ii) the crystal resulting from the annealed amorphous film of the compound, and (iii) the room-temperature crystals (alpha-phase) of the studied compounds were also obtained, fully assigned and correlated with intermolecular interactions present in the condensed phases, in particular H-bond interactions, showing that these latter are stronger in INA than in PA.