Ballistic ΔS=2 Intersystem Crossing in a Cobalt Cubane Following Ligand-Field Excitation Probed by Extreme Ultraviolet Spectroscopy

15 September 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Femtosecond M2,3-edge X-ray absorption near-edge structure (XANES) spectroscopy is used to probe the excited-state dynamics of the cobalt cubane [CoIII4O4](OAc)4(py)4 (OAc = acetate, py = pyridine), a model for water oxidation catalysts. After ligand-field excitation, intersystem crossing to a metal-centered quintet occurs in 38 fs. 30% of the hot quintet undergoes ballistic back-ISC directly to the singlet ground stat, with the remainder relaxing to a long-lived triplet.

Keywords

XANES spectroscopy
ultrafast
intersystem crossing
cobalt cubane
spin-crossover
XUV
extreme ultraviolet

Supplementary materials

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Description
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Electronic Supporting Information
Description
Further details concerning the XUV spectrometer, sample preparation, LFM simulations, and DFT calculations.
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