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A Direct Link from the Gas to the Condensed Phase: A Rotational Spectroscopic Study of 2,2,2‐Trifluoroethanol Trimers
Ist Teil von
Angewandte Chemie (International ed.), 2017-05, Vol.56 (22), p.6289-6293
Auflage
International ed. in English
Ort / Verlag
Germany: Wiley Subscription Services, Inc
Erscheinungsjahr
2017
Link zum Volltext
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
Rotational spectra of the three most stable conformers (I, II, III) of the ternary 2,2,2‐trifluoroethanol (TFE) cluster were measured using Fourier transform microwave spectrometers, and unambiguously assigned with the aid of ab initio calculations. The most stable conformer, I, contains one trans‐TFE subunit which is unstable in its isolated gas phase form. The study offers new insights into how the trans conformation is stabilized in TFE clusters of increasing size, and eventually becomes a dominant conformation in the liquid phase. A detailed analysis shows that while O−H⋅⋅⋅O−H and O−H⋅⋅⋅F−C hydrogen bonds are the most significant attractive interactions which stabilize all three conformers, the main driving force for the stability of I over III, which has all gauche‐TFE subunits, is the attractive interaction of C−F⋅⋅⋅F−C contact pairs. A new type of three‐point F⋅⋅⋅F⋅⋅⋅F attractive contact interaction is also identified.
Staying in contact: How trans‐2,2,2‐trifluoroethanol (TFE) becomes a significant conformation in the liquid phase while it is unstable in the isolated gas phase is a much‐debated topic. The experimental detection of a TFE trimer containing one trans‐TFE subunit shows that the attractive C−F⋅⋅⋅F−C contact interactions play a key role in preferential stabilization of trans versus gauche‐TFE in the trimer.