Monolayers of a thiacalix[3]pyridine-supported molybdenum(0) tricarbonyl complex on Au(111): characterisation with surface spectroscopy and scanning tunneling microscopy

Abstract

Deposition of dome-shaped metal–organic complexes on metallic surfaces to produce well-defined single site catalysts is a novel approach combining aspects of homogeneous and heterogeneous catalysis. In order to investigate the bonding of small molecules to such systems, a molybdenum(0) tricarbonyl complex supported by a thiacalix[3]pyridine is synthesized and deposited on Au(111) and Ag(111) surfaces by vacuum evaporation. The resulting mono- and submonolayers are investigated with surface spectroscopy and STM. All of these methods indicate a parallel orientation of the molybdenum complex with respect to the surface. The vibrational properties and frequency shifts of the adsorbed complexes with respect to the bulk are evaluated with the help of conventional IR and IRRA spectroscopy, coupled to DFT calculations. Compared to a similar Mo(0) tricarbonyl complex supported by an azacalixpyridine ligand, the title complex exhibits a higher stability in the bulk and adsorbed to surfaces which goes along with a lower reactivity towards oxygen.