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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...
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