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

Abstract

1,1,1,3,3,3‐hexafluoro‐propan‐2‐ol aggregates preferentially into an achiral dimer of achiral monomers, but the trimer is found to prefer three metastable chiral monomer units arranged into a strained OH⋅⋅⋅O hydrogen‐bonded ring, which is reinforced by secondary CH⋅⋅⋅FC interactions. This is shown by a combination of infrared, microwave, and Raman spectroscopy in supersonic jet expansions and supported by high‐level quantum chemical calculations. It involves an activation of the monomers by >15 kJ mol−1, clearly driven by the much stronger hydrogen‐bond interaction available to the gauche and even more to the cis monomer units.

Solid‐state synthesis of cyclo LD‐diphenylalanine: A chiral phase built from achiral subunits

“…Still, the molecule crystallizes as a chiral crystal endowed with a chiroptical response. This is an example of chirality synchronization, a phenomenon that has been observed also under isolated conditions . Surprisingly, always the same enantiomers of the 2‐propyl‐1‐H‐benzimidazole crystal is found whatever the experimental conditions.…”

Rovibronic signatures of molecular aggregation in the gas phase: subtle homochirality trends in the dimer, trimer and tetramer of benzyl alcohol

“…This preference can be inverted if attractive interactions between the residues become strong enough. Examples for the realization of this alternative 'bowl' arrangement with all three residues on the same side are the trimers of phenol, 12 2,2,2-trifluoroethanol, 69 1,1,1,3,3,3hexafluoro-propan-2-ol 70 and enantiopure methyl lactate. 71 This preference is also predicted for benzyl alcohol.…”

Sulfur hydrogen bonding and internal dynamics in the monohydrates of thenyl mercaptan and thenyl alcohol

“…Conformational changes induced by molecular aggregation have been occasionally reported. 48,49 From the energetic point of view two aspects are noticeable. The (B3LYP-D3(BJ)) complexation energies in Tables 1-2 Table 5 from a binding energy decomposition using SAPT(0)/jun-cc-pVDZ.…”