Disentangling the complex network of non-covalent interactions in fenchone hydrates via rotational spectroscopy and quantum chemistry

Abstract

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...

Setting up the HyDRA blind challenge for the microhydration of organic molecules

“…Among others, methanol 14 was not included into the core training set because of its very large amplitude internal motion and a capped phenylalanine 42 was not included because the global minimum hydrate structure presumably does not involve water as a hydrogen bond donor, although a higher-energy conformer does. Several ketones (cycloheptanone, cyclohexanone, 4,4-dimethylcyclohexanone, (À)-fenchone, 2-fluoroacetophenone, pinacolone, 3,3,5,5-tetramethylcyclohexanone) 43,44 were not included to keep the balance between represented functional groups. The growing set of non-selected submissions is still made available, with the goal of a comprehensive curated database on OH stretching wavenumbers of hydrate complexes in mind.…”

Setting up the HyDRA blind challenge for the microhydration of organic molecules

“…Among others, methanol 14 was not included into the core training set because of its very large amplitude internal motion and a capped phenylalanine 41 was not included because the global minimum hydrate structure presumably does not involve water as a hydrogen bond donor, although an energetically excited state does. Several ketones (cycloheptanone, cyclohexanone, 4,4-dimethylcyclohexanone, (-)-fenchone, 2-fluoroacetophenone, pinacolone, 3,3,5,5-tetramethylcyclohexanone) 42,43 were not included to keep the balance between represented functional groups. The growing set of nonselected submissions is still made available, with the goal of a comprehensive curated data base on OH stretching wavenumbers of hydrate complexes in mind.…”

Insights into the non-covalent interactions of hydrogen sulfide with fenchol and fenchone from a gas-phase rotational study

“…HB with water) was previously studied. 12,13 Both molecules showed relatively different hydration properties. For EF, only one monohydrate has been observed and the presence of a water molecule was found to alter the orientation of the hydroxyl group.…”

“…12 FEN is more capable of forming complexes with water, as several monohydrates, dihydrates, and trihydrates have been reported, without significant alteration of its most stable structure. 13 In this communication, we present the successful identification of the 1 : 1 complex of EF and FEN with H 2 S, based on the interplay between theoretical methods and experiments. Such a comprehensive study uses a combination of three different quantum chemical calculation methods with high-resolution rotational spectroscopy.…”