Combining high-resolution scanning tunnelling microscopy and first-principles simulations to identify halogen bonding

Lawrence, James, Sosso, Gabriele C., Đorđević, Luka, Pinfold, Harry, Bonifazi, Davide ORCID: https://orcid.org/0000-0001-5717-0121 and Costantini, Giovanni 2020. Combining high-resolution scanning tunnelling microscopy and first-principles simulations to identify halogen bonding. Nature Communications 11 , 2103. 10.1038/s41467-020-15898-2

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Abstract

Scanning tunnelling microscopy (STM) is commonly used to identify on-surface molecular self-assembled structures. However, its limited ability to reveal only the overall shape of molecules and their relative positions is not always enough to fully solve a supramolecular structure. Here, we analyse the assembly of a brominated polycyclic aromatic molecule on Au(111) and demonstrate that standard STM measurements cannot conclusively establish the nature of the intermolecular interactions. By performing high-resolution STM with a CO-functionalised tip, we clearly identify the location of rings and halogen atoms, determining that halogen bonding governs the assemblies. This is supported by density functional theory calculations that predict a stronger interaction energy for halogen rather than hydrogen bonding and by an electron density topology analysis that identifies characteristic features of halogen bonding. A similar approach should be able to solve many complex 2D supramolecular structures, and we predict its increasing use in molecular nanoscience at surfaces.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Schools > Chemistry
Publisher:	Nature Research
ISSN:	2041-1723
Date of First Compliant Deposit:	5 May 2020
Date of Acceptance:	24 March 2020
Last Modified:	06 Jan 2024 04:44
URI:	https://orca.cardiff.ac.uk/id/eprint/131447

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