A model is presented for the prediction of OH stretching fundamental wavenumbers of alcohol conformers in the gas phase by application of a small set of empirical anharmonicity corrections to...

By a combination of linear FTIR and Raman jet spectroscopy, racemic trans-1,2-cyclohexanediol is shown to form an energetically unrivalled S 4 -symmetric heterochiral dimer in close analogy to 1,2-ethanediol.Analogous experiments with enantiopure trans-1,2-cyclohexanediol reveal the spectral signature of at least three unsymmetric homochiral dimers. A comparison to signal-enhanced spectra of 1,2-ethanediol and to calculations uncovers at least three transiently homochiral dimer contributions as well. In few of these dimer structures, the intramolecular OHÁ Á ÁO contact present in monomeric 1,2-diols survives, despite the kinetic control in supersonic jet expansions. This provides further insights into the dimerisation mechanism of conformationally semi-flexible molecules in supersonic jets. Racemisation upon dimerisation is shown to be largely quenched under jet cooling conditions, whereas it should be strongly energy-driven at higher temperatures. The pronounced energetic preference for heterochiral aggregation of vicinal diols is also discussed in the context of chirality-induced spin selectivity. † Electronic supplementary information (ESI) available: Interactive and static structures, tables of experimental and computational details, energy diagrams for different levels of calculation, and additional experimental spectra. See

A combination of linear infrared and Raman spectroscopy in supersonic slit jet expansions is used to clarify the conformational preferences in the dimer of the transiently chiral benzyl alcohol (phenylmethanol)...

Molecular aggregation is of paramount importance in many chemical processes, including those in living beings. Thus, characterization of the intermolecular interactions is an important step on its understanding. We describe...

Complexes of t-butyl alcohol with norbornene and its monocyclic constituents cyclopentene and cyclohexene are studied via their OH stretching fundamental transitions in supersonic jet expansions. Compared to OH···OH hydrogen bonds, the spectral shifts due to OH···π bonding in the mixed dimers are reduced by a factor of 2. Mixed trimers show substantially different spectral signatures due to cooperative effects. Regioselective docking on the two sides of the double bond in norbornene is observed. Harmonic modeling of the spectra using dispersion-corrected hybrid functionals is quite successful, suggesting a high predictive power for this poorly explored class of complexes between alcohols and alkenes.