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Halogen bonding permeates many areas of chemistry. A wide range of halogen-bond donors including neutral, cationic, monovalent, and hypervalent have been developed and studied. In this work we used density functional theory (DFT), natural bond orbital (NBO) theory, and quantum theory of atoms in molecules (QTAIM) to analyze aryl halogen-bond donors that are neutral, cationic, monovalent and hypervalent and in each series we include the halogens Cl, Br, I, and At. Within this diverse set of halogen-bond donors, we have found trends that relate halogen bond length with the van der Waals radii of the halogen and the non-covalent or partial covalency of the halogen bond. We have also developed a model to calculate ΔGof halogen-bond formation by the linear combination of the % p-orbital character on the halogen and energy of the σ-hole on the halogen-bond donor.
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This content will become publicly available on June 11, 2026
Semicoordinate and halogen bonding to group 10 and group 8 metals
Although it has the geometric characteristics of a halogen bond, the binding between a square planar metal and a halogen atom rests primarily on transfer from the halogen lone pairs to the metal π-hole.
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- Award ID(s):
- 1954310
- PAR ID:
- 10624168
- Publisher / Repository:
- rsc
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- Volume:
- 27
- Issue:
- 23
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 12416 to 12426
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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