Conformational Landscapes of 2,3-, 2,4-, 2,5-, and 2,6-Difluorobenzaldehyde Unveiled by Rotational Spectroscopy.

ABSTRACT

We report the coexistence of anti-conformers and energetically unfavorable syn-conformers of 2,3-, 2,4-, 2,5-, and 2,6-difluorobenzaldehyde in the gas phase using broadband chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy. The rotational spectra of monosubstituted 13C isotopologues of the anti-conformers have also been assigned in natural abundance, which were used to derive their vibrationally averaged geometries and semi-experimental equilibrium structures. The energy differences between anti- and syn-conformations are estimated to be 10.9, 11.3, and 12.9 kJ/mol for 2,3-, 2,4-, and 2,5-difluorobenzaldehyde, respectively, at the theoretical level of DLPNO-CCSD(T)/def2-TZVP. Despite the steric repulsion caused by the close proximity between the oxygen atom of the aldehyde group and the ortho-substituted fluorine atom, our experimental results indicate the planarity of the syn-conformations. The frequencies of the large amplitude torsion between the phenyl and aldehyde groups have been estimated by experimental inertial defects, which agree with theoretical calculation results.