Delocalized relativistic effects, from the viewpoint of halogen bonding

Literature Information

Publication Date 2020-12-30
DOI 10.1039/D0CP05840H
Impact Factor 3.676
Authors

Serigne Sarr, Jérôme Graton, Seyfeddine Rahali, Gilles Montavon, Nicolas Galland


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Abstract

The ability of organic and inorganic compounds bearing both iodine and astatine atoms to form halogen-bond interactions is theoretically investigated. Upon inclusion of the relativistic spin–orbit interaction, the I-mediated halogen bonds are more affected than the At-mediated ones in many cases. This unusual outcome is disconnected from the behavior of iodine's electrons. The significant decrease of astatine electronegativity with the spin–orbit coupling triggers a redistribution of the electron density, which propagates relativistic effects toward the distant iodine atom. This mechanism can be controlled by introducing suitable substituents and, in particular, strengthened by taking advantage of electron-withdrawing inductive and mesomeric effects. Noticeable relativistic effects can actually be transferred to light atoms properties, e.g., the halogen-bond basicity of bridgehead carbon atoms doubled in propellane derivatives.

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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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