Three conformers of cyclooctanone have been identified by broadband rotational spectroscopy. Cyclooctanone shows a strong preference to adopt a boat-chair conformation, driven by minimisation of repulsive non-bonded transannular interactions.

The hydrates of the monoterpenoid fenchone (C10H16O).(H2O)n (n=1,2,3) were investigated both by computational chemistry and microwave spectroscopy. Two monohydrates, three dihydrates and for the first time three trihydrates have been...

The hydration of ketones is known to occur in condensed phases, but it is not considered to be favorable in the gas phase due to restricted water content. We report the first evidence of geminal diol formation upon ketone hydration in the gas phase, obtained through the investigation of the interactions of cyclooctanone with water using broadband rotational spectroscopy. Oxygen-atom exchange between water and cyclooctanone was observed for two isomers of cyclooctanone-H 2 O and two isomers of cyclooctanone-(H 2 O) 2 . All complexes were unambiguously identified from the analysis of the rotational spectrum of the parent species and all their 13 C and 18 O isotopologues, and their heavy-atom substitution and effective structures were determined as well as their binding interactions. The production of gem-diols from gas-phase hydration of ketones has implications for atmospheric chemistry and opens a new channel for secondary aerosol formation.

Non‐covalent interactions between molecules determine molecular recognition and the outcome of chemical and biological processes. Characterising how non‐covalent interactions influence binding preferences is of crucial importance in advancing our understanding of these events. Here, we analyse the interactions involved in smell and specifically the effect of changing the balance between hydrogen‐bonding and dispersion interactions by examining the complexes of the common odorant fenchone with phenol and benzene, mimics of tyrosine and phenylalanine residues, respectively. Using rotational spectroscopy and quantum chemistry, two isomers of each complex have been identified. Our results show that the increased weight of dispersion interactions in these complexes changes the preferred binding site in fenchone and sets the basis for a better understanding of the effect of different residues in molecular recognition and binding events.

The physicochemical properties and reactivity of macrocycles are critically shaped by their conformations. In this work, we have identified seven conformations of the macrocyclic ketone cyclododecanone using chirped-pulse Fourier transform microwave spectroscopy in combination with ab initio and density functional theory calculations. Cyclododecanone is strongly biased towards adopting a square configuration of the heavy atom framework featuring three C–C bonds per side. The substitution and effective structures of this conformation have been determined through the observation of its 13C isotopologues. The minimisation of transannular interactions and, to a lesser extent, HCCH eclipsed configurations drive conformational preferences. Our results contribute to a better understanding of the intrinsic forces mediating structural choices in macrocycles.