Self-Assembly of N-Rich Triimidazoles on Ag(111): Mixing the Pleasures and Pains of Epitaxy and Strain
Year: 2023
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide In the present report, homochiral hydrogen-bonded assemblies of heavily N-doped (C 9 H 6 N 6 ) heterocyclic triimidazole (TT) molecules on an Ag(111) substrate were investigated using scanning tunneling microscopy (STM) and low energy electron diffraction (LEED) techniques. The planar and prochiral TT molecules, which exhibit a threefold rotation symmetry and lack mirror symmetry when assembled on the substrate, carry multiple hydrogen-bonding donor and acceptor functionalities, inevitably leading to the formation of hexameric two-dimensionally extended assemblies that can be either homo- ( RR / SS ) or heterochiral ( RS ). Experimental STM data showing well-ordered homochiral domains and experimental LEED data are consistent with simulations assuming the 21 × 21 R 19.1° overlayer on the Ag(111) lattice. Importantly, we report the unexpected coincidence of spontaneous resolution with the condensation of neighboring islands in adjacent “Janus pairs”. The islands are connected by a characteristic fault zone, an observation that we discuss in the context of the fairly symmetric molecule and its propensity to compromise and benefit from interisland bonding at the expense of lattice mismatches and strain in the defect zone. We relate this to the close to triangular shape and the substantial but weak bonding scheme beyond van der Waals (vdW) of the TT molecules, which is due to the three N-containing five-membered imidazole rings. Density functional theory (DFT) calculations show clear energetic differences between homochiral and heterochiral pairwise interactions, clearly supporting the experimental results.
Institutions: University of Basel, Paul Scherrer Institute, University of Bern, National Institute for Research and Development of Isotopic and Molecular Technologies, École Polytechnique Fédérale de Lausanne, Istituto di Scienze e Tecnologie Chimiche "Giulio Natta", University of Milan, National Interuniversity Consortium of Materials Science and Technology, University of Salzburg
Language: English
Subfield: Biomedical Engineering
Field: Engineering
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $5,000
Funders: National Science Foundation, Universität Basel, University of Bern, Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung, Kommission für Technologie und Innovation, Paul Scherrer Institut, Ministerul Cercetării şi Inovării, Swiss Nanoscience Institute, Staatssekretariat für Bildung, Forschung und Innovation
Awards: G1305997238, G2251490852, G298171496, Scanning Tunneling Microscopy and Spectroscopy at variable Temperatures for the physical and chemical investigation of surface mounted supra-molecular assemblies., Thermal Desorption Mass Spectrometry for the Investigation of on-surface Chemistry and Supramolecular Chemistry, New Insight into Tip-Sample Interaction by Scanning Probe Methods, Nitrogenated Polycyclic Aromatic Hydrocarbons (N-PAHs): Nanostructures, Functionalization and Electronic Properties (NanoFun), Theoretical investigation of photocatalytic water splitting on surfaces and thin films of perovskite oxynitrides, G628552264, Opto-electronic and spintronic quantum transport in metal-organic nanowires and nanosheets, G777591065, Defect-induced functional properties in ferroic oxides
OpenAlex ID: W4388785413