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

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. 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.

Authors:
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)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1490675
Grant/Contract Number:  
AC02-76SF00515; 669531 EDAX
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 20; Journal Issue: 44; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Jay, Raphael M., Eckert, Sebastian, Fondell, Mattis, Miedema, Piter S., Norell, Jesper, Pietzsch, Annette, Quevedo, Wilson, Niskanen, Johannes, Kunnus, Kristjan, and Föhlisch, Alexander. The nature of frontier orbitals under systematic ligand exchange in (pseudo-)octahedral Fe(ii) complexes. United States: N. p., 2018. Web. doi:10.1039/c8cp04341h.
Jay, Raphael M., Eckert, Sebastian, Fondell, Mattis, Miedema, Piter S., Norell, Jesper, Pietzsch, Annette, Quevedo, Wilson, Niskanen, Johannes, Kunnus, Kristjan, & Föhlisch, Alexander. The nature of frontier orbitals under systematic ligand exchange in (pseudo-)octahedral Fe(ii) complexes. United States. doi:10.1039/c8cp04341h.
Jay, Raphael M., Eckert, Sebastian, Fondell, Mattis, Miedema, Piter S., Norell, Jesper, Pietzsch, Annette, Quevedo, Wilson, Niskanen, Johannes, Kunnus, Kristjan, and Föhlisch, Alexander. Thu . "The nature of frontier orbitals under systematic ligand exchange in (pseudo-)octahedral Fe(ii) complexes". United States. doi:10.1039/c8cp04341h. https://www.osti.gov/servlets/purl/1490675.
@article{osti_1490675,
title = {The nature of frontier orbitals under systematic ligand exchange in (pseudo-)octahedral Fe(ii) complexes},
author = {Jay, Raphael M. and Eckert, Sebastian and Fondell, Mattis and Miedema, Piter S. and Norell, Jesper and Pietzsch, Annette and Quevedo, Wilson and Niskanen, Johannes and Kunnus, Kristjan and Föhlisch, Alexander},
abstractNote = {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.},
doi = {10.1039/c8cp04341h},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 44,
volume = 20,
place = {United States},
year = {2018},
month = {9}
}

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Works referenced in this record:

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a