Structural and electronic effects of x-ray irradiation on prototypical [M(COD)Cl]2 catalysts

Journal article

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.

Authors: Fernando, NK; Cairns, AB; Murray, CA; Thompson, AL; Dickerson, JL

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: ACS Publications
• Journal: Journal of Physical Chemistry A
• Volume: 125
• Issue: 34
• Pages: 473–488
• Publication date: 2021-08-22
• DOI: 10.1021/acs.jpca.1c05759
• EISSN: 1520-5215
• ISSN: 1089-5639
• Pmid: 34420303
• Language: English
• Keywords: FFR