Π-Stacking in Heterodimers of Propargylbenzene with (Fluoro)phenylacetylenes

[Image: see text] The heterodimers of propargylbenzene (PrBz) with phenylacetylene (PHA) and monosubstituted fluorophenylacetylenes (FPHAs) were investigated using electronic and vibrational spectroscopic methods. The vibrational spectra in the acetylenic C–H stretching region show a marginal shift (0–4 cm(–1)) upon dimer formation, which suggests minimal perturbation of the acetylenic group. The M06-2X/aug-cc-pVDZ calculations indicate that the π-stacked structures are the most stable, followed by other structures. In general, structures incorporating aromatic C–H···π interactions are much higher in energy. The appearance of the spectra and the energy considerations clearly indicate the preference for the π-stacked structures. Furthermore, the observed trend in the stabilization energies for heterodimers with the three FPHAs is inversely proportional to the dipole moments of FPHAs. On the other hand, the absence of any clear trends in the electrostatic component of the interaction energy is attributed to the presence of the methylene group in PrBz.