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Title: The nature of frontier orbitals under systematic ligand exchange in (pseudo-)octahedral Fe(ii) complexes

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/c8cp04341h· OSTI ID:1490675
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [3];  [2];  [2];  [2];  [4];  [1]
  1. Univ. Potsdam, Potsdam (Germany); Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany)
  2. Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany)
  3. Stockholm Univ., Stockholm (Sweden)
  4. Stanford Univ., Menlo Park, CA (United States)
+ Show Author Affiliations

Understanding and controlling properties of transition metal complexes is a crucial step towards tailoring materials for sustainable energy applications. In a systematic approach, we use resonant inelastic X-ray scattering to study the influence of ligand substitution on the valence electronic structure around an aqueous iron(II) center. Exchanging cyanide with 2-2'-bipyridine ligands reshapes frontier orbitals in a way that reduces metal 3d charge delocalization onto the ligands. This net decrease of metal–ligand covalency results in lower metal-centered excited state energies in agreement with previously reported excited state dynamics. Furthermore, traces of solvent-effects were found indicating a varying interaction strength of the solvent with ligands of different character. Lastly, our results demonstrate how ligand exchange can be exploited to shape frontier orbitals of transition metal complexes in solution-phase chemistry; insights upon which future efforts can built when tailoring the functionality of photoactive systems for light-harvesting applications.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-76SF00515; 669531 EDAX
OSTI ID:
1490675
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Vol. 20, Issue 44; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 19 works
Citation information provided by
Web of Science

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Cited By (9)

Kovalenzgetriebene Erhaltung lokaler Ladungsdichten in einem durch Metall‐Ligand‐Ladungstransfer angeregten Eisenphotosensibilisator journal July 2019
Covalency-Driven Preservation of Local Charge Densities in a Metal-to-Ligand Charge-Transfer Excited Iron Photosensitizer journal July 2019
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering journal January 2020
Solvent-assisted structural conversion involving bimetallic complexes based on the tris(oxalato)ferrate( iii ) unit with the green → blue → red crystal color sequence journal January 2019
The restricted active space followed by second-order perturbation theory method: Theory and application to the study of CuO2 and Cu2O2 systems journal May 2008
Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering text January 2020
Covalency-Driven Preservation of Local Charge Densities in a Metal-to-Ligand Charge-Transfer Excited Iron Photosensitizer other January 2019
From the Free Ligand to the Transition Metal Complex: FeEDTA– Formation Seen at Ligand K-Edges journal June 2022
Tuning Excited State Electron Transfer in Fe Tetracyano-Polypyridyl Complexes preprint January 2019

Figures / Tables (5)

Fig. 1(p. 2)figure Fig. 1
Fig. 2(p. 3)figure Fig. 2
Fig. 4(p. 4)figure Fig. 4
Fig. 3(p. 7)figure Fig. 3
Table 1(p. 7)table Table 1

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