Fatty acids are ubiquitous in biological systems and widely used in materials science, including for the formulation of drugs and the surface-functionalization of nanoparticles. However, important questions regarding the structure and reactivity of these molecules are still to be elucidated, including their mode of binding to certain metal cations or materials surfaces. In this context, we have developed novel, efficient, user-friendly, and cost-effective synthetic protocols based on ball-milling, for the ¹⁷O and ¹⁸O isotopic labeling of two key fatty acids which are widely used in (nano)materials science, namely stearic and oleic acid. Labeled molecules were analyzed by ¹H and ¹³C solution NMR, IR spectroscopy, and mass spectrometry (ESI-TOF and LC-MS), as well as ¹⁷O solid state NMR (for the ¹⁷O labeled species). In both cases, the labeling procedures were scaled-up to produce up to gram quantities of ¹⁷O- or ¹⁸O-enriched molecules in just half-a-day, with very good synthetic yields (all ≥84%) and enrichment levels (up to an average of 46% per carboxylic oxygen). The ¹⁷O-labeled oleic acid was then used for the synthesis of a metal soap (Zn-oleate) and the surface-functionalization of ZnO nanoparticles (NPs), which were characterized for the first time by high-resolution ¹⁷O NMR (at 14.1 and 35.2 T). This allowed very detailed insight into (i) the coordination mode of the oleate ligand in Zn-oleate to be achieved (including information on Zn···O distances) and (ii) the mode of attachment of oleic-acid at the surface of ZnO (including novel information on its photoreactivity upon UV-irradiation). Overall, this work demonstrates the high interest of these fatty acid-enrichment protocols for understanding the structure and reactivity of a variety of functional (nano)materials systems using high resolution analyses like ¹⁷O NMR.

A porphyrin bearing four imidazolium rings on the meso positions was used as an N-heterocyclic carbene (NHC) precursor for the synthesis of porphyrin dimers with face-to-face orientations. The porphyrins are connected through the formation of eight M–C_NHC bonds, with M = Ag^I or Au^I.