TY  - JOUR
A1  - Jay, Raphael Martin
A1  - Eckert, Sebastian
A1  - Fondell, Mattis
A1  - Miedema, Piter S.
A1  - Norell, Jesper
A1  - Pietzsch, Annette
A1  - Quevedo, Wilson
A1  - Niskanen, Johannes
A1  - Kunnus, Kristjan
A1  - Föhlisch, Alexander
T1  - The nature of frontier orbitals under systematic ligand exchange in (pseudo-)octahedral Fe(II) complexes
JF  - Physical chemistry, chemical physics : a journal of European Chemical Societies
N2  - 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. 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.
Y1  - 2018
U6  - https://doi.org/10.1039/c8cp04341h
SN  - 1463-9076
SN  - 1463-9084
VL  - 20
IS  - 44
SP  - 27745
EP  - 27751
PB  - Royal Society of Chemistry
CY  - Cambridge
ER  - 
TY  - JOUR
A1  - Leitner, T.
A1  - Josefsson, Ida
A1  - Mazza, T.
A1  - Miedema, Piter S.
A1  - Schröder, H.
A1  - Beye, Martin
A1  - Kunnus, Kristjan
A1  - Schreck, S.
A1  - Düsterer, Stefan
A1  - Föhlisch, Alexander
A1  - Meyer, M.
A1  - Odelius, Michael
A1  - Wernet, Philippe
T1  - Time-resolved electron spectroscopy for chemical analysis of photodissociation
BT  - Photoelectron spectra of Fe(CO)(5), Fe(CO)(4), and Fe(CO)(3)
JF  - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
N2  - The prototypical photoinduced dissociation of Fe(CO)(5) in the gas phase is used to test time-resolved x-ray photoelectron spectroscopy for studying photochemical reactions. Upon one-photon excitation at 266 nm, Fe(CO)(5) successively dissociates to Fe(CO)(4) and Fe(CO)(3) along a pathway where both fragments retain the singlet multiplicity of Fe(CO)(5). The x-ray free-electron laser FLASH is used to probe the reaction intermediates Fe(CO)(4) and Fe(CO)(3) with time-resolved valence and core-level photoelectron spectroscopy, and experimental results are interpreted with ab initio quantum chemical calculations. Changes in the valence photoelectron spectra are shown to reflect changes in the valenceorbital interactions upon Fe-CO dissociation, thereby validating fundamental theoretical concepts in Fe-CO bonding. Chemical shifts of CO 3 sigma inner-valence and Fe 3 sigma core-level binding energies are shown to correlate with changes in the coordination number of the Fe center. We interpret this with coordination-dependent charge localization and core-hole screening based on calculated changes in electron densities upon core-hole creation in the final ionic states. This extends the established capabilities of steady-state electron spectroscopy for chemical analysis to time-resolved investigations. It could also serve as a benchmark for howcharge and spin density changes in molecular dissociation and excited-state dynamics are expressed in valence and core-level photoelectron spectroscopy. Published by AIP Publishing.
Y1  - 2018
U6  - https://doi.org/10.1063/1.5035149
SN  - 0021-9606
SN  - 1089-7690
VL  - 149
IS  - 4
PB  - American Institute of Physics
CY  - Melville
ER  -