Electronic Structure of Aqueous [Co(bpy)3]2+/3+ Electron Mediators
2019-04-15 | journal article
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Electronic Structure of Aqueous [Co(bpy)3]2+/3+ Electron Mediators
Sreekantan Nair Lalithambika, S.; Golnak, R.; Winter, B. & Atak, K. (2019)
Inorganic Chemistry, 58(8) pp. 4731-4740. DOI: https://doi.org/10.1021/acs.inorgchem.9b00167
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- Authors
- Sreekantan Nair Lalithambika, Sreeju; Golnak, Ronny; Winter, Bernd; Atak, Kaan
- 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.
- Issue Date
- 15-April-2019
- Journal
- Inorganic Chemistry
- Working Group
- RG Techert (Structural Dynamics in Chemical Systems)
- ISSN
- 0020-1669
- eISSN
- 1520-510X
- Language
- English