On-surface synthesis is a promising strategy for the preparation of molecules that are not achievable otherwise. Understanding the mechanism of on-surface reactions requires knowledge of the molecular structure and possible organization of reactants into supramolecular assemblies during the reaction. Scanning probe techniques are essential for the unambiguous identification of the products and for determining their electronic and magnetic properties. However, these are generally not capable of imaging the surface at reaction conditions and, therefore, answering some of the key questions about the reaction mechanism. Here, we show that real-time low-energy electron microscopy (LEEM) can monitor the surface processes in real time and provide the necessary complementary mechanistic insights into on-surface reactions. We monitor the intramolecular ring-closure reaction of 1,3,5-tris(7-methyl-α-carbolin-6-yl)benzene on the Au(111) surface and show that it takes place in the 2D molecular gas phase at elevated temperatures. Products condense into separate islands upon cooling, enabling fast and efficient assessment of product yields. This makes LEEM an efficient tool for studying intramolecular chemical reactions.

CEITEC Central European Institute of Technology Brno University of Technology Purkyňova 123 612 00 Brno Czech Republic

Department of Organic Chemistry University of Murcia Campus of Espinardo Murcia 30100 Spain

Faculty of Nuclear Sciences and Physical Engineering Czech Technical University Prague Břehová 78 7 11519 Prague 1 Czech Republic

Institute of Physical Engineering Brno University of Technology Technická 2896 2 616 69 Brno Czech Republic

Institute of Physics Czech Academy of Sciences Cukrovarnická 10 16200 Prague Czech Republic

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On-Surface Synthesis of a Large-Scale 2D MOF with Competing π-d Ferromagnetic/Antiferromagnetic Order