Design and testing of an (inert) gas cell for in situ polarization modulation infrared reflection absorption spectroscopic (PM-IRRAS) measurements under specific atmospheres.

Infrared reflection absorption spectroscopy (IRRAS) is a powerful surface-sensitive analytical technique to characterize the adsorbed molecules on metal surfaces down to (sub)monolayer coverage. In this paper, a new (inert) gas cell is presented that expands the scope of the commercially available Bruker PMA50 module. The cell is designed as a sample holder to measure thin films of molecules adsorbed on a metal substrate under a specific gaseous atmosphere.

Molybdenum(0)-Tricarbonyl Complex Supported by an Azacalix-pyridine Ligand: Synthesis, Characterization, Surface Deposition and Conversion to a Molybdenum(VI)-Trioxo Complex with O.

Adsorption of metal-organic complexes on metallic surfaces to produce well-defined single site catalysts is a novel approach combining the advantages of homogeneous and heterogeneous catalysis. To avoid the "surface trans-effect" a dome-shaped molybdenum(0) tricarbonyl complex supported by an tolylazacalix[3](2,6)pyridine ligand is synthesized. This vacuum-evaporable complex both activates CO and reacts with molecular oxygen (O) to form a Mo(VI) trioxo complex which in turn is capable of catalytically mediating oxygen transfer.

Oxidative Decarbonylation of an Azacalixpyridine-Supported Mo(0)-Tricarbonyl to a Mo(VI)-Trioxo Complex with Dioxygen in Solution and on Au(111): Determination of Molecular Mechanism.

The conversion of an azacalixpyridine-supported Mo(0) tricarbonyl into a Mo(VI) trioxo complex with dioxygen (O) is investigated in homogeneous solution and in a molecular film adsorbed on Au(111) using a variety of spectroscopic and analytical methods. These studies in particular show that the dome-shaped carbonyl complex adsorbed on the metal surface has the ability to bind and activate gaseous oxygen, overcoming the so-called surface trans-effect. Furthermore, the rate of the conversion dramatically increases by irradiation with light.

Improving the Switching Capacity of Glyco-Self-Assembled Monolayers on Au(111).

Self-assembled monolayers (SAMs) decorated with photoisomerizable azobenzene glycosides are useful tools for investigating the effect of ligand orientation on carbohydrate recognition. However, photoswitching of SAMs between two specific states is characterized by a limited capacity. The goal of this study is the improvement of photoswitchable azobenzene glyco-SAMs.