A Resilient Platform for the Discrete Functionalization of Gold Surfaces Based on N‑Heterocyclic Carbene Self-Assembled Monolayers

We describe the synthesis and characterization of a versatile platform for gold functionalization, based on self-assembled monolayers (SAMs) of distal-pyridine-functionalized N-heterocyclic carbenes (NHC) derived from bis­(NHC) Au­(I) complexes. The SAMs are characterized using polarization-modulation infrared reflectance-absorption spectroscopy, surface-enhanced Raman spectroscopy, and X-ray photoelectron spectroscopy. The binding mode is examined computationally using density functional theory, including calculations of vibrational spectra and direct comparisons to the experimental spectroscopic signatures of the monolayers. Our joint computational and experimental analyses provide structural information about the SAM binding geometries under ambient conditions. Additionally, we examine the reactivity of the pyridine-functionalized SAMs toward H2SO4 and W­(CO)5(THF) and verify the preservation of the introduced functionality at the interface. Our results demonstrate the versatility of N-heterocyclic carbenes as robust platforms for on-surface acid–base and ligand exchange reactions.