Forming N-heterocyclic carbene monolayers: not all deposition methods are the same†

N-Heterocyclic carbenes (NHCs) are unrivaled in their ability to form persistent and tunable monolayers on noble metal surfaces, with disciplines from heterogeneous catalysis to microelectronics fabrication rapidly adopting this technology. It is currently assumed that different NHC monolayer preparation protocols yield equivalent surfaces; however, a direct comparison of the leading synthetic protocols is yet to validate this assumption. Herein, we explore the binding of NHC ligands to gold (Au) surfaces prepared using the five most common NHC deposition methods and discover significant differences in the resulting monolayer composition and structure. In this work, NHC-Au systems are prepared according to literature procedures starting from either the free carbene, the CO₂ adduct, the bicarbonate salt, or the triflate salt. The resulting surfaces are characterized with surface-enhanced Raman spectroscopy (SERS), laser desorption/ionization mass spectrometry (LDI-MS), electrochemistry, and X-ray photoelectron spectroscopy (XPS). These data indicate that the free carbene, vacuum annealing, and solvent annealing methods form chemisorbed NHC monolayers, as expected; however, the solution phase methods without annealing yield surfaces with a fundamentally different character. Although XPS is widely used to confirm the binding of NHCs to metal surfaces, it does not capture the differences in these deposition procedures and should be used with caution. Taken together, these results reveal a significant variation of the NHC surface structure as a function of deposition procedure and provide a critical benchmark to govern the design and preparation of future NHC monolayer systems.