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
T2  - 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
UR  - https://publishup.uni-potsdam.de/frontdoor/index/index/docId/51161
SN  - 1463-9076
SN  - 1463-9084
VL  - 20
IS  - 44
SP  - 27745
EP  - 27751
PB  - Royal Society of Chemistry
CY  - Cambridge
ER  -