University of Illinois Urbana-Champaign

Characterization of photoinduced valence tautomerism in a cobalt dioxolene complex by femtosecond M-edge spectroscopy

Ash, Ryan T.

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1402674.pptx
3822.pdf

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https://hdl.handle.net/2142/104279

Description

Title
Characterization of photoinduced valence tautomerism in a cobalt dioxolene complex by femtosecond M-edge spectroscopy
Author(s)
Ash, Ryan T.
Contributor(s)
  • Vura-Weis, Josh
  • Zhang, Kaili
Issue Date
2019-06-19
Keyword(s)
High-harmonic generation and XUV spectroscopy
Date of Ingest
  • 2019-07-15T22:16:34Z
  • 2020-01-25T19:30:48Z
Abstract
Cobalt dioxolene complexes undergoing photoinduced valence tautomerism (VT) are potential candidates for molecular electronic devices. Thermal or photoinduced electron transfer between a dioxolene ligand and the metal center reversibly switch the complex between a paramagnetic or diamagnetic species. A low-spin Co$^{II}$ intermediate is believed to be involved in the photogeneration of the paramagnetic state from the diamagnetic state, but has not been spectroscopically observed yet. Our group has developed a tabletop M-edge XANES spectrometer which generates femtosecond extreme ultraviolet pulses via high-harmonic generation (HHG). M-edge spectroscopy has been shown to be sensitive to changes in oxidation state, spin state and/or ligand field changes at metal centers, and the spectra can be predicted using ligand field multiplet theory. In this work, we will present temperature dependent and time-resolved spectra of a cobalt dioxolene VT compound and highlight the ultrafast electron transfer and spin state changes. The theoretical tools developed to predict and interpret the M-edge spectra of metal-centered excited states will also be discussed. This work demonstrates that HHG-based XUV absorption spectroscopy is an accessible alternative to synchrotron-based X-ray absorption spectroscopy for elucidating the electronic structure and photoinduced dynamics of transition metal complexes.
Publisher
International Symposium on Molecular Spectroscopy
Type of Resource
text
Genre of Resource
Conference Paper / Presentation
Language
eng
Permalink
http://hdl.handle.net/2142/104279
DOI
https://doi.org/10.15278/isms.2019.WE02
Copyright and License Information
Copyright 2019 Ryan T. Ash

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Abstracts & Presentations - 2019 International Symposium on Molecular Spectroscopy PRIMARY