Quantitative chirality synchronization in trifluoroethanol dimers

Abstract

2,2,2-Trifluoroethanol molecules synchronize their transiently chiral gauche configurations upon dimerization in supersonic jet expansions, while they avoid an energetically competitive heteroconfigurational hydrogen bonded dimer topology predicted by extensive quantum chemical calculations.

Chirality Recognition between Neutral Molecules in the Gas Phase

“…Two different hydrogenbond topologies can be realized in the dimer. [196,197] The calculations predict an almost perfect energetic balance between an inserted structure with synchronized helicity and an addition structure with opposite helicity, separated by relatively high (! 5 kJ mol À1 ) barriers.…”

“…Nevertheless, even under the mildest jet relaxation conditions, only the inserted structure with constructive chirality synchronization could be detected (see Figure 14). Larger clusters show a tendency to stabilize trans conformations, [196] which are also quite abundant in the liquid. [198] Interestingly, such clusters of fluoroalcohols play an important role in accelerating stereospecific reactions of another helical molecule, HOOH, with olefins.…”

The Chiral Trimer and a Metastable Chiral Dimer of Achiral Hexafluoroisopropanol: A Multi‐Messenger Study

“…[5,6] Va cuum isolation and low temperatures can amplify the driving force for the adaptive aggregation by removing diluting solvation and entropy influences. [8] Theh omochiral dimer of trifluoroethanol has been particularly enigmatic,due to aheterochiral competitor very close in energy which was initially not observed at all [9] and later quantified at about 10 %i najet expansion experiment. [8] Theh omochiral dimer of trifluoroethanol has been particularly enigmatic,due to aheterochiral competitor very close in energy which was initially not observed at all [9] and later quantified at about 10 %i najet expansion experiment.…”

“…[7] Fluorous interactions appear to favor such processes. [8] Theh omochiral dimer of trifluoroethanol has been particularly enigmatic,due to aheterochiral competitor very close in energy which was initially not observed at all [9] and later quantified at about 10 %i najet expansion experiment. [10] Thet rimer of trifluoroethanol was recently shown to exhibit low-energy ring and chain conformations with different degrees of chirality synchronization.…”

Chirality effects in gas-phase spectroscopy and photophysics of molecular and ionic complexes: contribution of low and room temperature studies

“…In this respect, direct absorption by FTIR spectroscopy is a powerful tool as it is sensitive to all the species present in the jet [112]. Moreover, the study of complexes is facilitated by the gain in transition oscillator strength induced by hydrogen bond formation [113][114][115][116][117][118]. The small density of species as well as the weak oscillator strength inherent to IR spectroscopy makes the use of slit jets mandatory.…”