A new type of halogen bond involving multivalent astatine: an ab initio study

Literature Information

Publication Date 2019-06-17
DOI 10.1039/C9CP02406A
Impact Factor 3.676
Authors

Tian Lu, Qingyuan Yang, Yi Liu, Baishu Zheng


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Abstract

Theoretical studies on the dimers formed by CO with the halides of multivalent astatine as a Lewis-acid center are carried out to examine the typical characteristics of supervalent halogen bonds. Calculations at the MP2/aug-cc-pVTZ level reveal that the multiple nucleophilic sites of multivalent halide monomers can promote the formation of various types of halogen bonds, among which the most stable ones are At–halogen bond complexes with multivalent astatine as a Lewis acid center, followed by the π–halogen bond dimers, and the weakest ones are the X–halogen bonds. Compared with multivalent Cl-, Br-, and I-centers, At, as the heaviest halogen, exhibits the highest halogen-bond donating ability. We found that the electrostatic term and the dispersion term play an important role in the overall attractive interaction energy, and the smallest attraction term for all complexes is the polarization term (ΔEpol). Moreover, the tri and pentavalent halides analyzed here possess very “flexible” tautomerism in which the transformation occurs during the formation of the dimers. AIM theory and NBO analysis are also employed here.

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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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