Importance of water and intramolecular interaction governs substantial blue shift of Csp2 -H stretching frequency in complexes between chalcogenoaldehydes and water.

ABSTRACT

Geometrical structure, stability and cooperativity, and contribution of hydrogen bonds to the stability of complexes between chalcogenoaldehydes and water were thoroughly investigated using quantum chemical methods. The stability of the complexes increases significantly when one or more H2O molecules are added to the binary system, whereas it decreases sharply going from O to S, Se, or Te substitution. The O-H⋯O H-bond is twice as stable as Csp2 -H⋯O and O-H⋯S/Se/Te H-bonds. It is found that a considerable blue-shift of Csp2 -H stretching frequency in the Csp2 -H⋯O H-bond is mainly determined by an addition of water into the complexes along with the low polarity of the Csp2 -H covalent bond in formaldehyde and acetaldehyde. The Csp2 -H stretching frequency shift as a function of net second hyperconjugative energy for the σ*(Csp2 -H) antibonding orbital is observed. Remarkably, a considerable Csp2 -H blue shift of 109 cm-1 has been reported for the first time. Upon the addition of H2O into the binary systems, halogenated complexes witness a decreasing magnitude of the Csp2 -H stretching frequency blue-shift in the Csp2 -H⋯O H-bond, whereas CH3-substituted complexes experience the opposite trend.