The study of hydrogen bonding and π⋯π interactions in phenol⋯ethynylbenzene complex by IR spectroscopy.

Weak hydrogen bonds between phenol and ethynylbenzene in tetrachloroethene were explored by using FTIR spectroscopy. Association constants (Kc) were determined by high dilution method at two temperatures, 20°C and 26°C, and they are, respectively, 0.54±0.09 mol(-1) dm3 and 0.36±0.08 mol(-1) dm3. The position of ethynylbenzene stretching band, when in hydrogen bonding complex with phenol (CC⋯), is proposed to be governed by the interplay of OH⋯π (CC moiety or phenyl ring of ethynylbenzene) and π⋯π (phenyl ring of phenol⋯CC moiety or phenyl ring of ethynylbenzene) interactions. This conclusion is supported by the findings on the complex between ethanol and ethynylbenzene; in the latter, CC⋯ stretching band is shifted to the higher wavenumbers, as expected when ethynylbenzene interacts with hydrogen bond donor. Geometries and energies of the presumed complexes, as well as their vibrational spectra, are predicted by using ab initio calculations. The spectroscopic and thermodynamic data obtained here offer the missing pieces in the present picture of migration of H-atom of phenol OH group between competing hydrogen bond accepting centers on ethynylbenzene.