Growth of N‐Heterocyclic Carbene Assemblies on Cu(100) and Cu(111): From Single Molecules to Magic‐Number Islands

N‐Heterocyclic carbenes (NHCs) have superior properties as building blocks of self‐assembled monolayers (SAMs). Understanding the influence of the substrate in the molecular arrangement is a fundamental step before employing these ligands in technological applications. Herein, we study the molecular arrangement of a model NHC on Cu(100) and Cu(111). While mostly disordered phases appear on Cu(100), on Cu(111) well‐defined structures are formed, evolving from magic‐number islands to molecular ribbons with coverage. This work presents the first example of magic‐number islands formed by NHC assemblies on flat surfaces. Diffusion and commensurability are key factors explaining the observed arrangements. These results shed light on the molecule‐substrate interaction and open the possibility of tuning nanopatterned structures based on NHC assemblies.