Tip-induced nitrene generation

2025/06/05 by Leonard-Alexander Lieske, Lieske, Leonard-Alexander, Aaron H. Oechsle +14 · 1 citation
Engineering · Materials Science · #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Magnetism in coordination complexes #Materials Science (cond-mat.mtrl-sci) #Mesoscale and Nanoscale Physics (cond-mat.mes-hall) #Molecular Junctions and Nanostructures #Surface Chemistry and Catalysis

paper · pdf · doi:10.48550/arxiv.2506.04741

openalex publication_date 2025/06/05 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28

Abstract

We generated trinitreno-s-heptazine, a small molecule featuring three nitrene centers, by tip-induced chemistry from the precursor 2,5,8-triazido-s-heptazine on bilayer NaCl on Au(111). The precursor's azide groups were dissociated to form mono-, di- and trinitreno-s-heptazine, yielding molecules with one to three nitrene centers. The precursor and its products are characterized by atomic force microscopy and scanning tunnelling microscopy. Broken-symmetry DFT and configuration interaction calculations of inter- and intra-nitrene exchange couplings suggest a ferromagnetic coupling of the S = 1 nitrene centers, resulting in a high-spin septet ground state for neutral trinitreno-s-heptazine in the gas phase. On bilayer NaCl on Au(111), the combined results of experiments and theory suggest trinitreno-s-heptazine to be an anion with a sextet ground state.

Citations

• On-surface Synthesis of a Ferromagnetic Molecular Spin Trimer
• Anatomy of linear and non-linear intermolecular exchange in S = 1 nanographenes
• Topological design and synthesis of high-spin aza-triangulenes without Jahn-Teller distortions
• On-Surface Carbon Nitride Growth from Polymerization of 2,5,8-Triazido-s-heptazine
• The ORCA quantum chemistry program package
• CP2K: An electronic structure and molecular dynamics software package - Quickstep: Efficient and accurate electronic structure calculations
• Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals
• A consistent and accurateab initioparametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
• Snell’s Law for Surface Electrons: Refraction of an Electron Gas Imaged in Real Space
• Generalized Gradient Approximation Made Simple
• Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields

Cited by

• Skeletal editing by tip-induced chemistry

Related

• Developments in Arylnitrene Chemistry: Syntheses and Mechanisms [New synthetic methods (31)]
• Photogeneration and Visualization of a Surface‐Stabilized Dinitrene
• Tip-Induced Molecule Anchoring in Ni-Phthalocyanine on Au(111) Substrate
• Is phenylnitrene a missing link in the formation of polycyclic aromatic nitrogen heterocycles?
• Topological design and synthesis of high-spin aza-triangulenes without Jahn-Teller distortions