On-surface synthesis (OSS) offers unique opportunities for fabricating carbon-based nanostructures that are unattainable by conventional wet-chemical synthesis. Despite OSS being extremely successful, the use of coadsorbates to promote reactions remains largely unexplored. In this study, we investigate the role of sodium chloride (NaCl) in promoting the Scholl reaction (oxidative aryl-aryl coupling) of hexaazatriphenylene (HAT) molecules on Au(111), leading to the growth of conjugated azaacene oligomers. Using scanning tunneling microscopy (STM), synchrotron-based X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations, we shed light on the reaction mechanism and the intermediates involved. Upon codeposition on Au(111), NaCl decomposes on the surface, releasing Na atoms that form thermally stable metal-organic complexes, enhancing precursor stability against desorption. This stabilizing effect allows HAT molecules to undergo regioselective intermolecular coupling for polymerization at elevated temperatures. This study highlights the role of alkali metals in on-surface chemical reactions and outlines a strategy for overcoming the precursor-desorption issue.

CNR Istituto Officina dei Materiali TASC Laboratory Trieste 34149 Italy

Department of Chemistry and Catalysis Research Center Technical University of Munich 85748 Garching Germany

Department of Chemistry Biochemistry and Pharmaceutical Sciences W Inäbnit Laboratory for Molecular Quantum Materials and Werner Siemens Center for Molecular Quantum Systems University of Bern Bern 3012 Switzerland

Department of Chemistry Zhejiang Sci Tech University Hangzhou 310018 China

Department of Physical Chemistry University of Innsbruck Innsbruck 6020 Austria

Institute of Experimental and Applied Physics University of Regensburg 93053 Regensburg Germany

Institute of Physics of Czech Academy of Sciences Prague 16200 Czech Republic

Regional Centre of Advanced Technologies and Materials Czech Advanced Technology and Research Institute Palacký University Olomouc Olomouc 78371 Czech Republic

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