Monitoring On-Surface Chemical Reactions by Low-Energy Electron Microscopy: from Conformation Change to Ring Closure in 2D Molecular Gas.

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.