Revealing the Bonding of Solvated Ru Complexes with Valence-to-core Resonant Inelastic X-ray Scattering

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2021 Jun 24

PMID 34163645

Citations 9

Authors

Elisa Biasin

Daniel R Nascimento

Benjamin I Poulter

Baxter Abraham

Kristjan Kunnus

Angel T Garcia-Esparza

Stanislaw H Nowak

Thomas Kroll

Robert W Schoenlein

Roberto Alonso-Mori

Munira Khalil

Niranjan Govind

Dimosthenis Sokaras

Affiliations

Soon will be listed here.

Abstract

Ru-complexes are widely studied because of their use in biological applications and photoconversion technologies. We reveal novel insights into the chemical bonding of a series of Ru(ii)- and Ru(iii)-complexes by leveraging recent advances in high-energy-resolution tender X-ray spectroscopy and theoretical calculations. We perform Ru 2p4d resonant inelastic X-ray scattering (RIXS) to probe the valence excitations in dilute solvated Ru-complexes. Combining these experiments with a newly developed theoretical approach based on time-dependent density functional theory, we assign the spectral features and quantify the metal-ligand bonding interactions. The valence-to-core RIXS features uniquely identify the metal-centered and charge transfer states and allow extracting the ligand-field splitting for all the complexes. The combined experimental and theoretical approach described here is shown to reliably characterize the ground and excited valence states of Ru complexes, and serve as a basis for future investigations of ruthenium, or other 4d metals active sites, in biological and chemical applications.

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