Structural and Electronic Effects of X-ray Irradiation on Prototypical [M(COD)Cl](2) Catalysts

X-ray characterization techniques are invaluable for probing material characteristics and properties, and have been instrumental in discoveries across materials research. However, there is a current lack of understanding of how X-ray-induced effects manifest in small molecular crystals. This is of particular concern as new X-ray sources with ever-increasing brilliance are developed. In this paper, systematic studies of X-ray-matter interactions are reported on two industrially important catalysts, [Ir(COD)Cl](2) and [Rh(COD)Cl](2), exposed to radiation in X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) experiments. From these complementary techniques, changes to structure, chemical environments, and electronic structure are observed as a function of X-ray exposure, allowing comparisons of stability to be made between the two catalysts. Radiation dose is estimated using recent developments to the RADDOSE-3D software for small molecules and applied to powder XRD and XPS experiments. Further insights into the electronic structure of the catalysts and changes occurring as a result of the irradiation are drawn from density functional theory (DFT). The techniques combined here offer much needed insight into the X-ray-induced effects in transition-metal catalysts and, consequently, their intrinsic stabilities. There is enormous potential to extend the application of these methods to other small molecular systems of scientific or industrial relevance.

Automated summary

This paper presents systematic studies of X-ray-matter interactions on two industrially important catalysts through XRD and XPS experiments, revealing changes in structure and electronic structure due to X-ray exposure and allowing for comparisons of stability between the catalysts. Radiation dose was estimated using RADDOSE-3D software and applied to experiments, with further insights drawn from DFT. These methods have great potential for application to other small molecular systems of scientific or industrial relevance.