Vibrational dynamics of the salicylideneaniline molecule in the solid phase and the confined state

Matthieu Hureau (1) , Konstantin Smirnov (1) , Alain Moissette (1) , Hervé Jobic (2)

1 LASIRE - Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516
2 IRCELYON - Institut de recherches sur la catalyse et l'environnement de Lyon

The salicylideneaniline (SA) molecule, both in the solid phase and sorbed in silicalite-1 zeolite, was studied by a large palette of vibrational spectroscopic methods (INS, Raman, and infrared) and by computational techniques. The comparison of the experimental and calculated spectra unambiguously indicates that the molecule is present in the cis-enol form in both phases. The results of the study allowed the proposal of a complete assignment of the vibrational spectrum of the SA molecule. The analysis of peak positions in the Raman and INS spectra of the molecule in the solid and sorbed states, and of the corresponding vibrational modes, shows that the confinement by the zeolite mostly affects those modes whose vibrational amplitude is localized on atoms of the phenol ring. This finding suggests that the molecule sits in the zeolite void such that the phenol ring is affected by the sorption to a greater extent than the benzene one. This assumption is corroborated by results of molecular modeling that shows the most energetically preferred position of the molecule in the straight channel of the zeolite framework with the phenol ring lying between two channel intersections, whereas the benzene ring is situated in the intersection.

Domaines: Chimie théorique et/ou physique

Matthieu Hureau, Konstantin Smirnov, Alain Moissette, Hervé Jobic. Vibrational dynamics of the salicylideneaniline molecule in the solid phase and the confined state. Physical Chemistry Chemical Physics, 2014, 16 (16), pp.7562-7570. ⟨10.1039/c3cp54880e⟩. ⟨hal-00987449⟩