Conformational Isomerizations by Rotation around C-C or C-N Bonds: A Comparative Study on Matrix-Isolated Glycolamide and N-Hydroxyurea Excited with Near-IR Laser Light.

Abstract

Conformers and near-IR-induced conformational transformations were studied for monomers of glycolamide isolated in low-temperature matrixes. Two conformational isomers of the compound, Tt and Cc, were trapped from the gas phase into solid Ar matrixes. Selective near-IR excitation of glycolamide molecules adopting the Tt form led to the Tt → Cc conformational conversion. Analogously, selective near-IR excitation of Cc conformers resulted in the Cc → Tt transformation. Monochromatic near-IR light, generated by frequency-tunable laser sources, was used for irradiation of matrix-isolated monomers. Near-IR-induced Tt → Cc and Cc → Tt conformational transformations occurred upon excitation of 2νOH, 2νaNH2, and 2νsNH2 overtones, as well as upon excitation of νaNH2 + νsNH2 combination modes. In spite of the structural similarity of glycolamide and N-hydroxyurea, no conformational conversions were observed for monomers of the latter compound isolated in Ar matrixes and excited with near-IR light. The comparison of the effects of near-IR excitations of glycolamide and N-hydroxyurea demonstrates that transformations involving rotation of molecular fragments around a single C-C bond occur much easier than transformations involving rotation of the fragments around a C-N bond. The efficiency of the latter conversions is extremely low.