Electrostatically enhanced F⋯F interactions through hydrogen bonding, halogen bonding and metal coordination: an ab initio study

Literature Information

Publication Date 2016-07-04
DOI 10.1039/C6CP03862J
Impact Factor 3.676
Authors

Antonio Bauzá, Antonio Frontera


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Abstract

In this manuscript the ability of hydrogen and halogen bonding interactions, as well as metal coordination to enhance F⋯F interactions involving fluorine substituted aromatic rings has been studied at the RI-MP2/def2-TZVPD level of theory. We have used 4-fluoropyridine, 4-fluorobenzonitrile, 3-(4-fluorophenyl)propiolonitrile and their respective meta derivatives as aromatic compounds. In addition, we have used HF and IF as hydrogen and halogen bond donors, respectively, and Ag(I) as the coordination metal. Furthermore, we have also used HF as an electron rich fluorine donor entity, thus establishing F⋯F interactions with the above mentioned aromatic systems. Moreover, a CSD (Cambridge Structural Database) search has been carried out and some interesting examples have been found, highlighting the impact of F⋯F interactions involving aromatic fluorine atoms in solid state chemistry. Finally, cooperativity effects between F⋯F interactions and both hydrogen and halogen bonding interactions have been analyzed and compared. We have also used Bader's theory of “atoms in molecules” to further describe the cooperative effects.

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Source Journal

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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