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The rotational spectra of two isotopologues of the 1:1 complex between chlorotrifluoromethane and formaldehyde have been recorded and analyzed by using Fourier‐transform microwave spectroscopy. Only one rotamer was detected, with the two constituent molecules held together through a Cl⋅⋅⋅O halogen bond (RCl⋅⋅⋅O=3.048 Å). The dimer displays two simultaneous large‐amplitude intramolecular motions. The...
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