On the directionality of anion–π interactions

Literature Information

Publication Date 2011-02-10
DOI 10.1039/C0CP01894E
Impact Factor 3.676
Authors

Carolina Estarellas, Antonio Bauzá, Antonio Frontera, David Quiñonero, Pere M. Deyà


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Abstract

The directionality of two important noncovalent interactions involving aromatic rings (namely anion–π and cation–π) is investigated. It has been recently published that the anion–π interactions observed in X-ray structures where the anion is located exactly over the center of the ring are scarce compared to cation–π interactions. To explain this behavior, we have analyzed how the interaction energy (RI-MP2/aug-cc-pVDZ level of theory) is affected by moving the anion from the center of the ring to several directions in anion–π complexes of chloride with either hexafluorobenzene or trifluoro-s-triazine. We have compared the results with the directionality of the cation–π interaction in the sodium–benzene complex. The results are useful to explain the experimental differences between both ion–π interactions. We have also computed the van der Waals radii of several halide anions and we have compared them to the neutral halogen atoms.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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