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Martin Jarenmark

Martin Jarenmark

Research engineer

Martin Jarenmark

Visualizing the coordination-spheres of photoexcited transition metal complexes with ultrafast hard X-rays

Author

  • D. Khakhulin
  • L. M. Lawson Daku
  • D. Leshchev
  • G. E. Newby
  • M. Jarenmark
  • C. Bressler
  • M. Wulff
  • S. E. Canton

Summary, in English


The concept of coordination sphere (CS) is central to the rational development of hierarchical molecular assemblies in modern chemistry. Manipulating the organization around transition metal ions with covalent and supramolecular interactions is a general strategy that underlies most synthetic protocols. Achieving similar control for photoexcited molecular complexes is necessary to advance the design of light-driven functionalities. This objective calls for monitoring the ultrafast dynamics of the primary (1-CS) and the secondary (2-CS) coordination spheres on the atomic scale, which remains to date an important experimental challenge for short-lived species. In this work, transient wide-angle scattering of hard X-rays (25 keV) is employed with state-of-the-art AIMD simulations in order to visualize the 1-CS (solute-only) and the 2-CS (solvation cage) of the photoinduced high-spin (HS) state for [Fe(bpy)
3
]
2+
(bpy = 2,2′-bipyridine) in aqueous solution. Correlating this structural information in real-space reveals the interlacing of the two CS, which in turn explains why solvation affects the photoinduced electronic and structural dynamics in this class of complexes. More generally, these results obtained for a prominent prototypical system in ultrafast X-ray sciences demonstrate the unique perspectives offered by this technique to gain the crucial knowledge about the multiscale solvation dynamics that is currently missing for controlling the solute-solvent interactions in advanced functional nano and biomaterials employed for photoconversion.

Department/s

  • Lithosphere and Biosphere Science

Publishing year

2019

Language

English

Pages

9277-9284

Publication/Series

Physical Chemistry Chemical Physics

Volume

21

Issue

18

Document type

Journal article

Publisher

Royal Society of Chemistry

Topic

  • Theoretical Chemistry

Status

Published

ISBN/ISSN/Other

  • ISSN: 1463-9076