Despite the substantial success of N-heterocyclic carbenes (NHCs) as stable and versatile surface modification ligands, their use in nanoscale applications beyond chemistry is still hampered by the failure to control the carbene binding mode, which complicates the fabrication of monolayers with the desired physicochemical properties. Here, we applied vibrational sum-frequency generation spectroscopy to conduct a pseudokinetic surface analysis of NHC monolayers on Au thin films under ambient conditions. We observe for two frequently used carbene structures that their binding mode is highly dynamic and changes with the adsorption time. In addition, we demonstrate that this transition can be accelerated or decelerated to adjust the binding mode of NHCs, which allows fabrication of tailored monolayers of NHCs simply by kinetic control.
Keywords: N-heterocyclic carbenes; binding mode; kinetic control; self-assembly; sum-frequency generation.