Observation of transient high-valent states in the water oxidation catalyst CoIII4O4 cubane via extreme ultraviolet spectroscopy
Shari'ati, Yusef A.
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https://hdl.handle.net/2142/104340
Description
Title
Observation of transient high-valent states in the water oxidation catalyst CoIII4O4 cubane via extreme ultraviolet spectroscopy
Author(s)
Shari'ati, Yusef A.
Contributor(s)
Vura-Weis, Josh
Issue Date
2019-06-19
Keyword(s)
High-harmonic generation and XUV spectroscopy
Abstract
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The tetranuclear metal-oxo complex [Co$^{III}$$_{4}$O$_{4}$](OAc)$_{4}$(py)$_{4}$ is a homogeneous water oxidation catalyst and structural mimic of the oxygen evolving complex in photosynthetic organisms. The catalytic cycle involves a highly-oxidized intermediate the nature of which is controversial: leading formulations argue for either [Co$^{IV}$$_{2}$Co$^{III}$$_{2}$O$_{4}$] or [Co$^{V}$Co$^{III}$$_{3}$O$_{4}$].
We report the sensitization of the [Co$^{III}$$_{4}$O$_{4}$] cubane with a perylene bisimide dye thus enabling photoinduced electron transfer upon green light illumination and effecting a transient oxidation of the cobalt center(s). The resultant high-valent states and their dynamics are probed by ultrafast transient absorption and extreme ultraviolet (XUV) spectroscopies. XUV spectroscopy, by dint of its oxidation-state specificity, has the potential to reveal the true distribution of holes among cobalt centers within the oxidized cluster.
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