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Electronic Structure of Aqueous Co[bpy3]2+/3+ Electron Mediators

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Winter,  Bernd
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Citation

Lalithambika, S. S. N., Golnak, R., Winter, B., & Atak, K. (2019). Electronic Structure of Aqueous Co[bpy3]2+/3+ Electron Mediators. Inorganic Chemistry, 58(8), 4731-4740. doi:10.1021/acs.inorgchem.9b00167.


Cite as: http://hdl.handle.net/21.11116/0000-0003-432C-1
Abstract
We report on the electronic structure of cobalt (II) tris-2,2’-bipyridine and cobalt (III) tris-2,2’-bipyridine in aqueous solution using resonant inelastic X-ray scattering (RIXS) spectroscopy at the Co L-edge and N K-edge resonances. Partial fluorescence yield X-ray absorption spectra at both edges were obtained by signal integration of the respective RIXS spectra. Experiments are complemented by calculations of the X-ray absorption spectra for high and low spin configurations using density functional theory/restricted open shell configuration interaction singles and time-dependent density functional theory methods. We find that linear combinations of the simulated X-ray absorption spectra for different spin states reproduce the experimental spectra. Best agreement is obtained for measurements at the Co L-edge, for both samples. For cobalt (II) tris-2,2’-bipyridine our combined experimental and computational study reveals ~40% low-spin and ~60% high-spin state components. Much stronger low-spin character is found for cobalt (III) tris-2,2’-bipyridine, ~80% low spin and ~20% high spin. Prominent energy-loss features in the Co RIXS spectra are indicative of d–d excitations and charge-transfer excitations due to strong mixing between metal and ligand orbitals in both complexes. Analysis of N 1s RIXS data reveals the emission from metal dominated orbitals in the valence region, supporting the strong metal–ligand mixing.