Mapping the Ultrafast Changes of Continuous Shape Measures in Photoexcited Spin Crossover Complexes without Long-Range Order
(2015) In Journal of Physical Chemistry C 119(6). p.3322-3330- Abstract
- Establishing a tractable yet complete reaction coordinate for the spin-state interconversion in d(4)-d(7) transition metal complexes is an integral aspect of controlling the dynamics that govern their functionality. For spin crossover phenomena, the limitations of a single-mode approximation that solely accounts for an isotropic increase in the metal-ligand bond length have long been recognized for all but the simple octahedral monodentate FeII compounds. However, identifying the coupled deformations that also impact on the unimolecular rate constants remains experimentally and theoretically challenging, especially for samples that do not display long-range order or when crystallization profoundly alters the dynamics. Owing to the rapid... (More)
- Establishing a tractable yet complete reaction coordinate for the spin-state interconversion in d(4)-d(7) transition metal complexes is an integral aspect of controlling the dynamics that govern their functionality. For spin crossover phenomena, the limitations of a single-mode approximation that solely accounts for an isotropic increase in the metal-ligand bond length have long been recognized for all but the simple octahedral monodentate FeII compounds. However, identifying the coupled deformations that also impact on the unimolecular rate constants remains experimentally and theoretically challenging, especially for samples that do not display long-range order or when crystallization profoundly alters the dynamics. Owing to the rapid progress in ultrafast X-ray absorption spectroscopy (XAS), it is now possible to obtain transient structural information in any physical phase with unprecedented details. Using picosecond XAS and DFT modeling, the structure adopted by the photoinduced high-spin state of solvated [Fe(terpy)(2)](2+) (terpy: 2,2':6',2 ''-terpyridine) has been recently established. Based on these results, the methodology of the continuous shape measure is applied to classify and quantify the short-lived distortion of the first coordination shell. The reaction coordinate of the spin-state interconversion is clearly identified as a double axial bending. This finding sets a benchmark for gauging the influence of first-sphere and second-sphere interactions in the family of FeII complexes that incorporate terpy derivatives. Some implications for the optimization of related photoactive FeII complexes are also outlined. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/5160173
- author
- Canton, Sophie LU ; Zhang, X. ; Daku, M. L. Lawson ; Liu, Yizhu LU ; Zhang, J. and Alvarez, S.
- organization
- publishing date
- 2015
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of Physical Chemistry C
- volume
- 119
- issue
- 6
- pages
- 3322 - 3330
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000349578400047
- scopus:84923169407
- ISSN
- 1932-7447
- DOI
- 10.1021/jp5117189
- 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: Chemical Physics (S) (011001060), Centre for Analysis and Synthesis (011001266)
- id
- 122854b2-a0e0-4e8f-bf1e-d1d5417cfe2b (old id 5160173)
- date added to LUP
- 2016-04-01 10:40:32
- date last changed
- 2022-02-17 20:16:13
@article{122854b2-a0e0-4e8f-bf1e-d1d5417cfe2b,
abstract = {{Establishing a tractable yet complete reaction coordinate for the spin-state interconversion in d(4)-d(7) transition metal complexes is an integral aspect of controlling the dynamics that govern their functionality. For spin crossover phenomena, the limitations of a single-mode approximation that solely accounts for an isotropic increase in the metal-ligand bond length have long been recognized for all but the simple octahedral monodentate FeII compounds. However, identifying the coupled deformations that also impact on the unimolecular rate constants remains experimentally and theoretically challenging, especially for samples that do not display long-range order or when crystallization profoundly alters the dynamics. Owing to the rapid progress in ultrafast X-ray absorption spectroscopy (XAS), it is now possible to obtain transient structural information in any physical phase with unprecedented details. Using picosecond XAS and DFT modeling, the structure adopted by the photoinduced high-spin state of solvated [Fe(terpy)(2)](2+) (terpy: 2,2':6',2 ''-terpyridine) has been recently established. Based on these results, the methodology of the continuous shape measure is applied to classify and quantify the short-lived distortion of the first coordination shell. The reaction coordinate of the spin-state interconversion is clearly identified as a double axial bending. This finding sets a benchmark for gauging the influence of first-sphere and second-sphere interactions in the family of FeII complexes that incorporate terpy derivatives. Some implications for the optimization of related photoactive FeII complexes are also outlined.}},
author = {{Canton, Sophie and Zhang, X. and Daku, M. L. Lawson and Liu, Yizhu and Zhang, J. and Alvarez, S.}},
issn = {{1932-7447}},
language = {{eng}},
number = {{6}},
pages = {{3322--3330}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Journal of Physical Chemistry C}},
title = {{Mapping the Ultrafast Changes of Continuous Shape Measures in Photoexcited Spin Crossover Complexes without Long-Range Order}},
url = {{http://dx.doi.org/10.1021/jp5117189}},
doi = {{10.1021/jp5117189}},
volume = {{119}},
year = {{2015}},
}