Conformational Space and Photochemistry of Tyramine Isolated in Argon and Xenon Cryomatrixes

The infrared spectra of tyramine monomers trapped in low-temperature argon and xenon matrixes were recorded. The presence of the flexible ethylamino side chain gives rise to a complex conformational surface that contains several minima of relatively low energies, some of them stabilized by a weak N-H···pi hydrogen bond interaction between the amino group and the phenyl ring. The experimental infrared spectra confirm the presence of at least two stable conformers isolated in the matrixes. Annealing experiments performed on the xenon matrix revealed a change in the relative population of the experimentally relevant conformers upon isolation in this polarizable matrix, compared to the gas phase. The general interpretation of the spectra was based on harmonic and anharmonic quantum chemical calculations, undertaken at the DFT/B3LYP and MP2 levels of theory with the 6-311++G(d,p) basis set. The photochemical behavior of the matrix-isolated compound upon narrow-band UV irradiation was also investigated. Identification of ketene species in the spectra of the irradiated matrixes suggests the occurrence of a ring-opening reaction, which in the xenon matrix occurs concomitantly with the conformational isomerization of tyramine