Abstract
Tailoring the surface composition of ionic liquids (ILs) is a key strategy for enhancing the performance of supported ionic liquid phase (SILP) catalysts. Here, we investigate the interfacial behavior of fluorine-free Ru polypyridyl complexes functionalized with n-nonyl side chains (Ru-C(9)) dissolved in two ILs with contrasting physicochemical properties, such as hydrophobicity and surface tension, namely [C(4)C(1)Im][PF(6)] and [C(4)C(1)Im][OAc]. Using angle-resolved X-ray photoelectron spectroscopy (ARXPS), we show that Ru-C(9) complexes undergo pronounced surface enrichment in [C(4)C(1)Im][PF(6)], adopting a buoy-like orientation at the IL/vacuum interface. Surface saturation is achieved at a bulk concentration of 0.12%(mol), a regime relevant for efficient SILP catalysis. In contrast, no interfacial enrichment is observed in [C(4)C(1)Im][OAc], highlighting the critical role of IL composition, particularly anion identity and surface tension, in governing the surface distribution of metal complexes. These findings provide molecular-level insights into the design of IL-based catalytic systems with optimized interfacial properties.