title: Molecular structure, vibrational spectra, quantum chemical calculations and photochemistry of picolinamide and isonicotinamide isolated in cryogenic inert matrixes and in the neat low-temperature solid phases.
abstract: 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.
authors: Department of Chemistry, University of Coimbra, P-3004-535, Portugal.
authors: Ana
authors: A
authors: Borba
authors: Andrea
authors: A
authors: Gómez-Zavaglia
authors: R
authors: R
authors: Fausto
mesh_terms: D000577:Amides / Q000737:chemistry; D003080:Cold Temperature; D006860:Hydrogen Bonding; D015394:Molecular Structure; D009536:Niacinamide / Q000737:chemistry*; D010777:Photochemistry; D010848:Picolinic Acids / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D000577:Amides; D010848:Picolinic Acids; D009536:Niacinamide; C027681:isonicotinamide; C003142:picolinamide