MONITORING ELECTRON DELOCALIZATION IN A MIXED VALENCE RU DIMER USING TRANSIENT RU L-EDGE X-RAY AND INFRARED SPECTROSCOPIES

Poulter, Benjamin I

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Description

Title

MONITORING ELECTRON DELOCALIZATION IN A MIXED VALENCE RU DIMER USING TRANSIENT RU L-EDGE X-RAY AND INFRARED SPECTROSCOPIES

Author(s)

Poulter, Benjamin I

Contributor(s)

• Liekhus-Schmaltz, Chelsea
• Schoenlein, Robert
• Alonso Mori, Roberto
• Sokaras, Dimosthenis
• Reinhard, Marco
• Cordones-Hahn, Amy
• Milne, Christopher
• Cirelli, Claudio
• Knopp, Gregor
• Johnson, Philip
• Arrell, Christopher
• Ozerov, Dmitry
• Usov, Ivan
• Augustin, Sven
• Govind, Niranjan
• Ghosh, Soumen
• Biasin, Elisa
• Khalil, Munira
• Sandwisch, Jason
• Weakly, Robert

Issue Date

2023-06-20

Keyword(s)

Mini-symposium: Spectroscopy at Large-scale Facilities

Abstract

Recent spectro-electrochemical studies have shown that the Ru-Ru dimer, [Ru(tpy)(bpy)(µ-CN)Ru(bpy)₂(CH₃CN)]³⁺(tpy = terpyridine, bpy = bipyridine), exhibits Class III mixed valency (complete delocalization between metal centers) upon one electron oxidation. Photochemically, this could be achieved by metal-to-ligand-charge transfer (MLCT) excitation where one Ru center is oxidized while one of the polypyridine ligands is reduced. Characterizing the extent of electron delocalization on the excited states of donor-bridge-acceptor complexes remains an important target in the field of mixed-valence chemistry. Transient X-ray spectroscopies are well suited to investigate electron delocalization processes as they offer element and orbital specific probes of local electronic and atomic structure. Here, we utilized solution phase, femtosecond, Ru L₃-edge resonant inelastic X-ray scattering, performed at the Alvra Prime end station of the Swiss X-ray Free Electron Laser, to probe valence electron and hole motions during the ultrafast delocalization process following MLCT excitation. A complementary study using transient Infrared spectroscopy was done to determine role of the CN bridge in the delocalization process. Additionally, TD-DFT calculations of spectroscopic observables were performed to help interpret and describe the X-ray and infrared experiments.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

Text

Language

eng

Handle URL

https://hdl.handle.net/2142/122663

DOI

https://doi.org/10.15278/isms.2023.7192

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