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

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Abstract

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.

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

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Publication details

The article was received on 10 Jul 2018, accepted on 31 Aug 2018 and first published on 13 Sep 2018


Article type: Paper
DOI: 10.1039/C8CP04341H
Citation: Phys. Chem. Chem. Phys., 2018, Advance Article
  • Open access: Creative Commons BY-NC license
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    The nature of frontier orbitals under systematic ligand exchange in (pseudo-)octahedral Fe(II) complexes

    R. M. Jay, S. Eckert, M. Fondell, P. S. Miedema, J. Norell, A. Pietzsch, W. Quevedo, J. Niskanen, K. Kunnus and A. Föhlisch, Phys. Chem. Chem. Phys., 2018, Advance Article , DOI: 10.1039/C8CP04341H

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