TY - JOUR
T1 - Cs+–π interactions and the design of macrocycles for the capture of environmental radiocesium (Cs-137)
T2 - DFT, QTAIM, and CSD studies
AU - Pichierri, Fabio
N1 - Funding Information:
Acknowledgements The author acknowledges the useful scientific discussions with and feedback from the attendees of the XLIII Congress of Theoretical Chemists of Latin Expression (CHITEL 2017) held in Paris on July 3–7, 2017. Also, the anonymous reviewers of this paper are gratefully acknowledged for their comments and useful suggestions. I thank the financial support from the Department of Applied Chemistry of the Graduate School of Engineering of Tohoku University and the Japan Society for the Promotion of Science (JSPS) “Grants-in-Aid for Scientific Research” (Kakenhi-C) Nr. 15K05580.
Publisher Copyright:
© 2018, Springer-Verlag GmbH Germany, part of Springer Nature.
Copyright:
Copyright 2018 Elsevier B.V., All rights reserved.
PY - 2018/8/1
Y1 - 2018/8/1
N2 - Using a combination of density functional theory and the quantum theory of atoms in molecules, we investigate the nature of the Cs+–π interaction in two types of model complexes. The models considered herein are the charged Cs+–arene system and the neutral Cs+–arene–I− system. In either model, the electron-withdrawing substituents on the arene moiety do compete with the Cs+ ion that interacts equally with the six carbon atoms of the arene. When an iodide ion is present, its electronic charge density is made available to the arene and then transferred to the alkali metal cation, thus enhancing its binding energy. In addition to these models, the complexes of Cs+ with the tetraphenylborate anion and calixarenes are investigated starting from the corresponding molecular crystal structures retrieved from the Cambridge Structural Database. These complexes are characterized by the presence of multiple Cs+–π interactions which increase the overall binding energy of the alkali metal cation. Our computational results are expected to provide useful guidelines for the design of macrocycles for the selective recognition and efficient extraction of radiocesium (Cs-137) in contaminated fluids.
AB - Using a combination of density functional theory and the quantum theory of atoms in molecules, we investigate the nature of the Cs+–π interaction in two types of model complexes. The models considered herein are the charged Cs+–arene system and the neutral Cs+–arene–I− system. In either model, the electron-withdrawing substituents on the arene moiety do compete with the Cs+ ion that interacts equally with the six carbon atoms of the arene. When an iodide ion is present, its electronic charge density is made available to the arene and then transferred to the alkali metal cation, thus enhancing its binding energy. In addition to these models, the complexes of Cs+ with the tetraphenylborate anion and calixarenes are investigated starting from the corresponding molecular crystal structures retrieved from the Cambridge Structural Database. These complexes are characterized by the presence of multiple Cs+–π interactions which increase the overall binding energy of the alkali metal cation. Our computational results are expected to provide useful guidelines for the design of macrocycles for the selective recognition and efficient extraction of radiocesium (Cs-137) in contaminated fluids.
KW - Cesium
KW - Chemical bonding
KW - Critical point analysis
KW - Environmental radioactivity
KW - Ion recognition
KW - Molecular structure
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U2 - 10.1007/s00214-018-2298-9
DO - 10.1007/s00214-018-2298-9
M3 - Article
AN - SCOPUS:85050973118
VL - 137
JO - Theoretical Chemistry Accounts
JF - Theoretical Chemistry Accounts
SN - 1432-881X
IS - 8
M1 - 118
ER -