Alkynes as CH/π Acceptors: Microwave Spectra and Structures of the CH<sub>2</sub>F<sub>2</sub>···Propyne and CH<sub>2</sub>ClF···Propyne Dimers ErnstAnthony A. ChristenholzCori L. DhahirYasser J. PeeblesSean A. PeeblesRebecca A. 2015 Rotational spectra of weakly bound complexes of chlorofluoromethane (CH<sub>2</sub>ClF) and difluoromethane (CH<sub>2</sub>F<sub>2</sub>) with propyne (HCCCH<sub>3</sub>) have been measured using chirped-pulse and resonant-cavity Fourier-transform microwave spectroscopy, adding to a relatively small body of high resolution spectroscopic data on propyne complexes. Both dimers contain CH/π contacts, as well as secondary contacts between one or both halogen atoms and the methyl group of propyne. A detailed structural determination for CH<sub>2</sub>F<sub>2</sub>···propyne has been made by study of the normal, one deuterated and four <sup>13</sup>C substituted isotopologues, with the second lowest energy configuration predicted from <i>ab initio</i> calculations agreeing well with the observed structure. Experimental rotational constants for the most abundant isotopologue of CH<sub>2</sub>F<sub>2</sub>···propyne are <i>A</i><sub>00</sub> = 5815.5858(15) MHz, <i>B</i><sub>00</sub> = 1341.1191(5) MHz, <i>C</i><sub>00</sub> = 1099.2040(4) MHz (uncorrected for internal rotation effects), and the dipole moment components, determined by Stark effect measurements, are μ<sub><i>a</i></sub> = 1.568(2) D, μ<sub><i>b</i></sub> = 0.587(2) D, and μ<sub>tot</sub> = 1.674(3) D. For CH<sub>2</sub>ClF···propyne, only <sup>35</sup>Cl and <sup>37</sup>Cl isotopologues have been assigned, providing rotational constants and chlorine atom coordinates consistent with the lowest energy structure from a series of <i>ab initio</i> predictions. Rotational constants for the <sup>35</sup>Cl isotopologue are <i>A</i> = 3423.639(7) MHz, <i>B</i> = 1253.7562(20) MHz, and <i>C</i> = 1200.4828(15) MHz and the diagonal and two off diagonal components of the quadrupole coupling tensor have also been determined.