Journal Article

PUBDB-2019-04736

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Electronic Structure of Aqueous $[Co(bpy)_{3}]^{2+/3+}$ Electron Mediators

Sreekantan Nair Lalithambika, S. (Corresponding author)DESY* ; Golnak, R. ; Winter, B. ; Atak, K. (Corresponding author)DESY*

2019
American Chemical Society Washington, DC

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Please use a persistent id in citations: doi:10.1021/acs.inorgchem.9b00167  doi:10.3204/PUBDB-2019-04736

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.

Note: © American Chemical Society

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Contributing Institute(s):

1. Strukturdynamik Chemischer Systeme (FS-SCS)
2. DOOR-User (DOOR ; HAS-User)

Research Program(s):

1. 6215 - Soft Matter, Health and Life Sciences (POF3-621) (POF3-621)
2. 6G3 - PETRA III (POF3-622) (POF3-622)

Experiment(s):

1. PETRA Beamline P11 (PETRA III)
2. PETRA Beamline P24 (PETRA III)

Appears in the scientific report 2019

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Database coverage:
; ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; IF < 5 ; JCR ; NCBI Molecular Biology Database ; Nationallizenz ; SCOPUS ; Science Citation Index ; Science Citation Index Expanded ; Web of Science Core Collection

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