The Macrocycle versus Chain Competition in On‐Surface Polymerization: Insights from Reactions of 1,3‐Dibromoazulene on Cu(111)

Ring/chain competition in oligomerization reactions represents a long‐standing topic of synthetic chemistry and was treated extensively for solution reactions but is not well‐understood for the two‐dimensional confinement of surface reactions. Here, the kinetic and thermodynamic principles of ring/chain competition in on‐surface synthesis are addressed by scanning tunneling microscopy, X‐ray photoelectron spectroscopy, and Monte Carlo simulations applied to azulene‐based organometallic oligomers on Cu(111). Analysis of experiments and simulations reveals how the ring/chain ratio can be controlled through variation of coverage and temperature. At room temperature, non‐equilibrium conditions prevail and kinetic control leads to preferential formation of the entropically favored chains. In contrast, high‐temperature equilibrium conditions are associated with thermodynamic control, resulting in increased yields of the energetically favored rings. The optimum conditions for ring formation include the lowest possible temperature within the regime of thermodynamic control and a low coverage. The general implications are discussed and compared to the solution case.