Probing the Anisotropic Distortion of Photoexcited Spin Crossover Complexes with Picosecond X-ray Absorption Spectroscopy
(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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- author
- organization
- publishing date
- 2014
- 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 (ACS)
- external identifiers
-
- wos:000332188100079
- scopus:84896875459
- ISSN
- 1932-7447
- DOI
- 10.1021/jp5003963
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Centre for Analysis and Synthesis (011001266), Chemical Physics (S) (011001060), Department of Chemistry (011001220)
- id
- b3bcd3b2-0b65-41db-a779-6e02a1d619e7 (old id 4414363)
- date added to LUP
- 2016-04-01 10:51:28
- date last changed
- 2022-01-26 03:06:34
@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 (ACS)}}, 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}}, doi = {{10.1021/jp5003963}}, volume = {{118}}, year = {{2014}}, }