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Title: Mapping the Ultrafast Changes of Continuous Shape Measures in Photoexcited Spin Crossover Complexes without Long-Range Order

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 andmore » 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

Authors:
 [1];  [2];  [3];  [4];  [5];  [6]
  1. Department of Synchrotron Radiation Instrumentation, Lund University, P.O. Box 118, 22100 Lund, Sweden
  2. X-ray Sciences Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
  3. Département de Chimie Physique, Université de Genève, Quai E. Ansermet 30, CH-1211 Genève 4, Switzerland
  4. Centre for Analysis and Synthesis, Department of Chemistry, Lund University, S-22100 Lund, Sweden
  5. School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, China
  6. Departament de Química Inorgànica and Institut de Química Teòrica i Computacional, Universitat de Barcelona, Martí i Franqués 1-11, 08028 Barcelona, Spain
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1392009
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. C; Journal Volume: 119; Journal Issue: 6
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Canton, S. E., Zhang, X., Lawson Daku, M. L., Liu, Y., Zhang, J., and Alvarez, S. Mapping the Ultrafast Changes of Continuous Shape Measures in Photoexcited Spin Crossover Complexes without Long-Range Order. United States: N. p., 2015. Web. doi:10.1021/jp5117189.
Canton, S. E., Zhang, X., Lawson Daku, M. L., Liu, Y., Zhang, J., & Alvarez, S. Mapping the Ultrafast Changes of Continuous Shape Measures in Photoexcited Spin Crossover Complexes without Long-Range Order. United States. doi:10.1021/jp5117189.
Canton, S. E., Zhang, X., Lawson Daku, M. L., Liu, Y., Zhang, J., and Alvarez, S. Fri . "Mapping the Ultrafast Changes of Continuous Shape Measures in Photoexcited Spin Crossover Complexes without Long-Range Order". United States. doi:10.1021/jp5117189.
@article{osti_1392009,
title = {Mapping the Ultrafast Changes of Continuous Shape Measures in Photoexcited Spin Crossover Complexes without Long-Range Order},
author = {Canton, S. E. and Zhang, X. and Lawson Daku, M. L. and Liu, Y. and Zhang, J. and Alvarez, S.},
abstractNote = {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.},
doi = {10.1021/jp5117189},
journal = {Journal of Physical Chemistry. C},
number = 6,
volume = 119,
place = {United States},
year = {Fri Jan 30 00:00:00 EST 2015},
month = {Fri Jan 30 00:00:00 EST 2015}
}