PM-IRRAS and DFT investigation of the surface orientation of new Ir piano-stool complexes attached to Au(111)

Surface immobilization of organometallic catalysts is a promising approach to developing new catalytic systems that combine molecular catalysts with heterogenous surfaces to probe surface mechanisms. The orientation of the catalyst relative to the surface is one important parameter that must be considered in such hybrid systems. In this work, we synthesize three new sulfide-modified Ir piano-stool complexes with sulfide-modified bipyridine and phenylpyridine ligands for the attachment to Au(111) surfaces. Self-assembled monolayers made from (Cp*Ir(2,2′-bipyridine-4-sulfide)Cl) 2 [Cl] 2 ( C1m ) and [Cp*Ir(2-phenylpyridine-4-sulfide)Cl] 2 ( C2m ) were characterized by combining polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) with DFT calculations of the minimum energy orientations of the complexes on the surface. We find that the bipyridine and phenylpyridine ligands are oriented at between 7377 relative to the surface normal, irrespective of the orientation of the other ligands. Additionally, DFT and PM-IRRAS support that there is no orientation preference for C1m and C2m , with both orientations present on the surface. Detailed characterization and understanding of Ir piano-stool catalysts immobilized on gold surfaces are a necessary first step in understanding new heterogenized catalytic systems at interfaces.