Journal article
Authors list: Henkel, Pascal; Pohl, Kiyan Linus Haiko; Mollenhauer, Doreen
Publication year: 2024
Pages: 5848-5859
Journal: Journal of Physical Chemistry C
Volume number: 128
Issue number: 14
ISSN: 1932-7447
eISSN: 1932-7455
DOI Link: https://doi.org/10.1021/acs.jpcc.3c07555
Publisher: American Chemical Society
Abstract:
The halogen bonding concept is well established and states that the strength of the halogen bond increases with the polarizability of the halogen. Recent experimental studies of aromatics halogenated with bromine and iodine on the Cu(111) surface showed that the known order Br < I can be reversed to Br > I. To understand this reversal effect of the halogen bond strength in more detail, we performed model calculations of the halogen bond with bromo/iodobenzene on (111) coinage metal surfaces (Cu, Ag, Au) using density functional theory. We characterized the strength of the halogen bond on the coinage metal surfaces as well as in the gas phase. In addition, we investigated the influence of the coinage metal surfaces on the inclination of the sigma holes. The study shows an inclination of the iodine sigma hole of iodobenzene in contrast to bromobenzene. This effect occurs almost exclusively on Cu(111) and is only slightly present on Ag(111), while it does not occur on Au(111). Furthermore, we found that the tilt is independent of the adsorption position (top, bridge, fcc, and hcp hollow site). As a result of the tilting of the iodine sigma hole, the halogen bond on Cu(111) is weakened, leading to an inversion of the halogen bond strength. Thus, on Cu(111) the halogen bond strength is Br > I, contrary to the well-known trend, whereas on Ag(111) and Au(111), it is I > Br, in line with the well-known trend.
Citation Styles
Harvard Citation style: Henkel, P., Pohl, K. and Mollenhauer, D. (2024) Influence of the Coinage Metal(111) Surface on the Orientation of the σ Hole and the Halogen Bonding Strength of Bromo/Iodobenzene, Journal of Physical Chemistry C, 128(14), pp. 5848-5859. https://doi.org/10.1021/acs.jpcc.3c07555
APA Citation style: Henkel, P., Pohl, K., & Mollenhauer, D. (2024). Influence of the Coinage Metal(111) Surface on the Orientation of the σ Hole and the Halogen Bonding Strength of Bromo/Iodobenzene. Journal of Physical Chemistry C. 128(14), 5848-5859. https://doi.org/10.1021/acs.jpcc.3c07555