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Probing the Anisotropic Distortion of Photoexcited Spin Crossover Complexes with Picosecond X-ray Absorption Spectroscopy

Canton, Sophie LU ; Zhang, Xiaoyi; Daku, Latevi M. Lawson; Smeigh, Amanda L.; Zhang, Jianxin LU ; Liu, Yizhu LU ; Wallentin, Carl-Johan LU ; Attenkofer, Klaus; Jennings, Guy and Kurtz, Charles A., et al. (2014) In Journal of Physical Chemistry C 118(8). p.4536-4545
Abstract
For numerous spin crossover complexes, the anisotropic distortion of the first coordination shell around the transition metal center governs the dynamics of the high-spin/low-spin interconversion. However, this structural parameter remains elusive for samples that cannot be investigated with crystallography. The present work demonstrates how picosecond X-ray absorption spectroscopy is able to capture this specific deformation in the photoinduced high-spin state of solvated [Fe(terpy)(2)](2+), a complex which belongs to the prominent family of spin crossover building blocks with nonequivalent metal-ligand bonds. The correlated changes in Fe-N-Axial, Fe-N-Distal, and bite angle N-Distal-Fe-N-Axial extracted from the measurements are in very... (More)
For numerous spin crossover complexes, the anisotropic distortion of the first coordination shell around the transition metal center governs the dynamics of the high-spin/low-spin interconversion. However, this structural parameter remains elusive for samples that cannot be investigated with crystallography. The present work demonstrates how picosecond X-ray absorption spectroscopy is able to capture this specific deformation in the photoinduced high-spin state of solvated [Fe(terpy)(2)](2+), a complex which belongs to the prominent family of spin crossover building blocks with nonequivalent metal-ligand bonds. The correlated changes in Fe-N-Axial, Fe-N-Distal, and bite angle N-Distal-Fe-N-Axial extracted from the measurements are in very good agreement with those predicted by DFT calculations in D-2d symmetry. The outlined methodology is generally applicable to the characterization of ultrafast nuclear rearrangements around metal centers in photoactive molecular complexes and nanomaterials, including those that do not display long-range order. (Less)
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type
Contribution to journal
publication status
published
subject
in
Journal of Physical Chemistry C
volume
118
issue
8
pages
4536 - 4545
publisher
The American Chemical Society
external identifiers
  • wos:000332188100079
  • scopus:84896875459
ISSN
1932-7447
DOI
10.1021/jp5003963
language
English
LU publication?
yes
id
b3bcd3b2-0b65-41db-a779-6e02a1d619e7 (old id 4414363)
date added to LUP
2014-04-30 08:19:59
date last changed
2017-08-27 03:36:23
@article{b3bcd3b2-0b65-41db-a779-6e02a1d619e7,
  abstract     = {For numerous spin crossover complexes, the anisotropic distortion of the first coordination shell around the transition metal center governs the dynamics of the high-spin/low-spin interconversion. However, this structural parameter remains elusive for samples that cannot be investigated with crystallography. The present work demonstrates how picosecond X-ray absorption spectroscopy is able to capture this specific deformation in the photoinduced high-spin state of solvated [Fe(terpy)(2)](2+), a complex which belongs to the prominent family of spin crossover building blocks with nonequivalent metal-ligand bonds. The correlated changes in Fe-N-Axial, Fe-N-Distal, and bite angle N-Distal-Fe-N-Axial extracted from the measurements are in very good agreement with those predicted by DFT calculations in D-2d symmetry. The outlined methodology is generally applicable to the characterization of ultrafast nuclear rearrangements around metal centers in photoactive molecular complexes and nanomaterials, including those that do not display long-range order.},
  author       = {Canton, Sophie and Zhang, Xiaoyi and Daku, Latevi M. Lawson and Smeigh, Amanda L. and Zhang, Jianxin and Liu, Yizhu and Wallentin, Carl-Johan and Attenkofer, Klaus and Jennings, Guy and Kurtz, Charles A. and Gosztola, David and Wärnmark, Kenneth and Hauser, Andreas and Sundström, Villy},
  issn         = {1932-7447},
  language     = {eng},
  number       = {8},
  pages        = {4536--4545},
  publisher    = {The American Chemical Society},
  series       = {Journal of Physical Chemistry C},
  title        = {Probing the Anisotropic Distortion of Photoexcited Spin Crossover Complexes with Picosecond X-ray Absorption Spectroscopy},
  url          = {http://dx.doi.org/10.1021/jp5003963},
  volume       = {118},
  year         = {2014},
}