Skip to Main content Skip to Navigation
Journal articles

Astatine Facing Janus: Halogen Bonding vs. Charge-Shift Bonding

Abstract : The nature of halogen-bond interactions was scrutinized from the perspective of astatine, potentially the strongest halogen-bond donor atom. In addition to its remarkable electronic properties (e.g., its higher aromaticity compared to benzene), C6At6 can be involved as a halogen-bond donor and acceptor. Two-component relativistic calculations and quantum chemical topology analyses were performed on C6At6 and its complexes as well as on their iodinated analogues for comparative purposes. The relativistic spin–orbit interaction was used as a tool to disclose the bonding patterns and the mechanisms that contribute to halogen-bond interactions. Despite the stronger polarizability of astatine, halogen bonds formed by C6At6 can be comparable or weaker than those of C6I6. This unexpected finding comes from the charge-shift bonding character of the C–At bonds. Because charge-shift bonding is connected to the Pauli repulsion between the bonding σ electrons and the σ lone-pair of astatine, it weakens the astatine electrophilicity at its σ-hole (reducing the charge transfer contribution to halogen bonding). These two antinomic characters, charge-shift bonding and halogen bonding, can result in weaker At-mediated interactions than their iodinated counterparts.
Document type :
Journal articles
Complete list of metadata

http://hal.univ-nantes.fr/hal-03346537
Contributor : Nicolas Galland Connect in order to contact the contributor
Submitted on : Thursday, September 16, 2021 - 2:13:46 PM
Last modification on : Monday, October 11, 2021 - 9:20:04 AM

Files

GallandNicolas_2021.pdf
Publisher files allowed on an open archive

Identifiers

Citation

Serigne Sarr, Julien Pilmé, Gilles Montavon, Jean-Yves Le Questel, Nicolas Galland. Astatine Facing Janus: Halogen Bonding vs. Charge-Shift Bonding. Molecules, MDPI, 2021, 26 (15), pp.4568. ⟨10.3390/molecules26154568⟩. ⟨hal-03346537⟩

Share

Metrics

Record views

69

Files downloads

117