Perturbation of hydrogen bonding in hydrated pyrrole-2-carboxaldehyde complexes

J Mol Model. 2017 Jul;23(7):216. doi: 10.1007/s00894-017-3380-2. Epub 2017 Jun 30.

Abstract

The interaction of external water molecules with hydrated pyrrole-2-carboxaldehyde PCL/(H2O) n complexes was investigated. The work was supported by both theoretical [DFT/TD-DFT methods using 6-311G++(d,p) basis set in the ground (S0) and excited (S1, S2, S3)states] and experimental [UV-Vis, FTIR and Raman] verification. The focus of the present work was on the weak intermolecular O-H⋯O, N-H⋯O-H hydrogen bonded interaction (IerHB) between PCL and external water molecules, and the influence of increasing the number of water molecules to form hydrated PCL/(H2O)n complexes. Effects were observed on different vibrational normal modes and on electronic transition levels. A hydrogen-bonded network of water induces a shift to higher energy in certain normal modes of PCL to form stable PCL/(H2O)n complexes by lowering the barrier energy. Potential energy distribution (PED) analysis indicates a significant charge transfer from PCL to water by creating a water bridge. Hydrogen bonding effects account for the substantial red shift and broadness in νNH, νCO vibrational modes. Water rearrangement turns out to be the main driving force for hydrated complex formation. Graphical abstract Stability of PCL/(H2O)4 hydarted complex.

Keywords: Hydrated PCL/(H2O) n complex; IerHB; Stability; Vibrational spectra.