Home > Publications database > Electronic Structure of Aqueous $[Co(bpy)_{3}]^{2+/3+}$ Electron Mediators > print

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024 7 _ |a 10.1021/acs.inorgchem.9b00167
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|a Sreekantan Nair Lalithambika, Sreeju
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245 _ _ |a Electronic Structure of Aqueous $[Co(bpy)_{3}]^{2+/3+}$ Electron Mediators
260 _ _ |a Washington, DC
|b American Chemical Society
|c 2019
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520 _ _ |a 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.
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700 1 _ |a Golnak, Ronny
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700 1 _ |a Winter, Bernd
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|a Atak, Kaan
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|g Vol. 58, no. 8, p. 4731 - 4740
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