Effect of aromatic ring fluorination on CH⋯π interactions: microwave spectrum and structure of the 1,2-difluorobenzene⋯acetylene dimer

• Published in: Physical chemistry chemical physics : PCCP 2016, Vol.18 (35), p.24290-24298
• Main Authors: Akmeemana, Anuradha G., Kang, Justin M., Dorris, Rachel E., Nelson, Rebecca D., Anderton, Ashley M., Peebles, Rebecca A., Peebles, Sean A., Seifert, Nathan A., Pate, Brooks H.
• Format: Article
• Language: English
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/C6CP04737H

Rotational spectra for the normal isotopic species and for six additional isotopologues of the 1,2-difluorobenzene⋯acetylene (C 6 H 4 F 2 ⋯HCCH) weakly bound dimer have been assigned in the 6–18 GHz region using chirped-pulse Fourier-transform microwave spectroscopy. This is the third complex in a series of fluorinated benzene⋯acetylene dimers. In 1,2-difluorobenzene⋯HCCH, the H⋯π distance (2.725(28) Å) is longer by about 0.23 Å, and the estimated binding energy ( E B = 2.3(6) kJ mol −1 ) is weaker by about 1.8 kJ mol −1 , than in the previously studied fluorobenzene⋯HCCH complex. In addition, in 1,2-difluorobenzene⋯acetylene, HCCH tips ∼46(3)° away from perpendicular to the aromatic ring, with the H nearest the ring moving away from the fluorine atoms along the C 2 axis of the monomer, while in the fluorobenzene and benzene complexes HCCH is perpendicular (benzene⋯HCCH) or nearly perpendicular (fluorobenzene⋯HCCH, ∼7° tilt) to the ring plane. Results from ab initio and DFT calculations will be compared to an experimental structure determined from rotational constants for the DCCD and five unique 13 C substituted isotopologues.