TY - JOUR
T1 - Water Arrangements upon Interaction with a Rigid Solute
T2 - Multiconfigurational Fenchone-(H2O)4-7 Hydrates
AU - Burevschi, Ecaterina
AU - Chrayteh, Mhamad
AU - Murugachandran, S. Indira
AU - Loru, Donatella
AU - Dréan, Pascal
AU - Sanz, M. Eugenia
N1 - Funding Information:
The authors thank funding from UE FP7 (Marie Curie grant PCIG12-GA-2012-334525), EPSRC (EP/N509498/1), and King\u2019s College London. Funding was also provided by the French ANR Labex CaPPA (through the PIA under contract ANR-11-LABX-0005-01), the Regional Council Hauts de France, the European Funds for Regional Economic Development (FEDER), and the French Ministe\u0300re de l\u2019Enseignement Supe\u0301rieur et de la Recherche. It is a contribution to the CPER research Project CLIMIBIO.
Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.
PY - 2024/4/8
Y1 - 2024/4/8
N2 - Insight into the arrangements of water molecules around solutes is important to understand how solvation proceeds and to build reliable models to describe water-solute interactions. We report the stepwise solvation of fenchone, a biogenic ketone, with 4-7 water molecules. Multiple hydrates were observed using broadband rotational spectroscopy, and the configurations of four fenchone-(H2O)4, three fenchone-(H2O)5, two fenchone-(H2O)6, and one fenchone-(H2O)7 complexes were characterized from the analysis of their rotational spectra in combination with quantum-chemical calculations. Interactions with fenchone deeply perturb water configurations compared with the pure water tetramer and pentamer. In two fenchone-(H2O)4 complexes, the water tetramer adopts completely new arrangements, and in fenchone-(H2O)5, the water pentamer is no longer close to being planar. The water hexamer interacts with fenchone as the least abundant book isomer, while the water heptamer adopts a distorted prism structure, which forms a water cube when including the fenchone oxygen in the hydrogen bonding network. Differences in hydrogen bonding networks compared with those of pure water clusters show the influence of fenchone’s topology. Specifically, all observed hydrates except one show two water molecules binding to fenchone through each oxygen lone pair. The observation of several water arrangements for fenchone-(H2O)4-7 complexes highlights water adaptability and provides insight into the solvation process.
AB - Insight into the arrangements of water molecules around solutes is important to understand how solvation proceeds and to build reliable models to describe water-solute interactions. We report the stepwise solvation of fenchone, a biogenic ketone, with 4-7 water molecules. Multiple hydrates were observed using broadband rotational spectroscopy, and the configurations of four fenchone-(H2O)4, three fenchone-(H2O)5, two fenchone-(H2O)6, and one fenchone-(H2O)7 complexes were characterized from the analysis of their rotational spectra in combination with quantum-chemical calculations. Interactions with fenchone deeply perturb water configurations compared with the pure water tetramer and pentamer. In two fenchone-(H2O)4 complexes, the water tetramer adopts completely new arrangements, and in fenchone-(H2O)5, the water pentamer is no longer close to being planar. The water hexamer interacts with fenchone as the least abundant book isomer, while the water heptamer adopts a distorted prism structure, which forms a water cube when including the fenchone oxygen in the hydrogen bonding network. Differences in hydrogen bonding networks compared with those of pure water clusters show the influence of fenchone’s topology. Specifically, all observed hydrates except one show two water molecules binding to fenchone through each oxygen lone pair. The observation of several water arrangements for fenchone-(H2O)4-7 complexes highlights water adaptability and provides insight into the solvation process.
UR - http://www.scopus.com/inward/record.url?scp=85189922294&partnerID=8YFLogxK
U2 - 10.1021/jacs.4c01891
DO - 10.1021/jacs.4c01891
M3 - Article
AN - SCOPUS:85189922294
SN - 0002-7863
VL - 146
SP - 10925
EP - 10933
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 15
ER -