Self-assembled monolayers (SAMs) of N-heterocyclic carbenes (NHCs) on metallic substrates are at present probably the most promising techniques in context of molecular-scale engineering of surfaces and interfaces, essential for quite a few purposes. Curiosity in NHC SAMs is principally pushed by their assumingly greater thermal stability in comparison with thiolate SAMs most broadly used in the intervening time. Many of the NHC SAMs make the most of imidazolium as an anchoring group for linking molecules to the metallic substrate by way of carbene C atom. It’s properly established within the literature that standing up and secure NHC SAMs are constructed solely when utilizing cumbersome aspect teams hooked up to nitrogen heteroatoms in imidazolium moiety, which, nonetheless, results in monolayers exhibiting a lot decrease packing density in comparison with thiolate SAMs. Right here, by mixed X-ray photoelectron spectroscopy, near-edge X-ray absorption effective construction spectroscopy, and temperature-programmed secondary ion mass spectrometry evaluation, we display that utilizing NHCs with small methyl aspect teams together with easy, solution-based preparation results in the formation of fragrant monolayers exhibiting at the very least doubled floor density, upright molecular orientation, and ultra-high thermal stability in comparison with the NHC SAMs reported earlier than. These parameters are essential for many purposes, together with, particularly, molecular and natural electronics, the place fragrant SAMs serve both as a passive aspect for electrode engineering or as an lively a part of natural subject impact transistors and novel molecular electronics units.