How to Get Them on: N‐Heterocyclic Carbenes (NHCs) on Surfaces

ABSTRACT N‐Heterocyclic carbenes (NHCs) have emerged as powerful and versatile surface‐modifiers, forming robust and tunable metal–organic interfaces. Their controlled generation and attachment remain central to advancing NHC‐based surface chemistry, as free carbenes are reactive species. This mini‐review highlights current strategies for generating NHCs under conditions compatible with surface functionalization, including direct deprotonation of azolium salts, thermal activation of stable CO 2 and bicarbonate adducts, and emerging electrochemical methods. Here, the structure–reactivity relationships governing precursor stability and activation behavior, and their implementation in vacuum and solution environments, are discussed. Techniques used to study the modified surfaces are also briefly presented. Together, these developments provide a foundation for designing clean, well‐defined NHC monolayers, enabling new opportunities in various domains, including catalysis, sensing, and molecular electronics.