Sub-Angstrom Imaging of Nondegenerate Kekulé Structures in a Two-Dimensional Halogen-Bonded Supramolecular Network
J. Phys. Chem. C 126, 4241–4247(2022)
Haohan Li, Mykola Telychko, Linwei Zhou, Zhi Chen, Xinnan Peng, Wei Ji, Jiong Lu & Kian Ping Loh
Abstract
Formation of a two-dimensional (2D) supramolecular self-assembly and a 2D organometallic framework derived from a brominated N-heterocyclic aromatic molecule (4Br-TAP) on Au(111) and Ag(111) substrates were studied using chemical bond-resolved scanning tunneling microscopy (STM) and noncontact atomic force microscopy (ncAFM) techniques combined with density functional theory (DFT) calculations. The 4Br-TAP-based 2D molecular framework on Au(111) is constructed by diverse Br···Br and Br···N noncovalent interactions, which are resolved with sub-angstrom resolution using combined STM and ncAFM imaging with a CO-functionalized tip and further quantified using DFT calculations. The distortion of molecular backbones, triggered by a highly nonuniform bonding environment, leads to lifting of the degeneracy of the intrinsic resonance structures of tetraazapyrene (TAP) moieties and emergence of two chiral Kekulé-like structures. In contrast, debromination of 4Br-TAP on Ag(111) leads to the formation of an ordered 2D organometallic framework linked by C–Ag–C bonds. Our results underpin the tremendous potential of the tip-functionalized ncAFM technique for microscopic identification of a complex interplay of intermolecular interactions and their associated impact on the molecular resonance structures.
