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Title: Resolving the Ultrafast Changes of Chemically Inequivalent Metal–Ligand Bonds in Photoexcited Molecular Complexes with Transient X-ray Absorption Spectroscopy

Abstract

Photoactive transition-metal complexes that incorporate heteroleptic ligands present a fast coordination shell, which is asymmetric. While it is generally expected that the metal-ligand bond lengths respond differently to photoexcitation, resolving these fine structural changes remains experimentally challenging, especially for flexible multidentate ligands. Here, ultrafast X-ray absorption spectroscopy is employed to capture directly the asymmetric elongations of chemically inequivalent metal-ligand bonds in the photoexcited spin-switching Fe-II complex [Fe-II(tpen)](2+) solvated in acetonitrile, where tpen denotes N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethylenediamine. The possibility to correlate precisely the nature of the donor/acceptor coordinating atoms to specific photoinduced structural changes within a binding motif will provide advanced diagnostics for optimizing numerous photoactive chemical and biological building blocks.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3];  [2];  [2]; ORCiD logo [4]; ORCiD logo [5]
  1. Tianjin Polytechnic Univ., (China)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
  3. UNAM-IIM Morelia (Mexico)
  4. Univ. of Geneva (Switzerland)
  5. ELI-HU Non-Profit Ltd., Szeged (Hungary); ; Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Natural Science Foundation of China (NNSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
OSTI Identifier:
1532536
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Omega
Additional Journal Information:
Journal Volume: 4; Journal Issue: 4; Journal ID: ISSN 2470-1343
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 73 NUCLEAR PHYSICS AND RADIATION PHYSICS

Citation Formats

Zhang, Jianxin, Zhang, Xiaoyi, Suarez-Alcantara, Karina, Jennings, Guy, Kurtz, Charles A., Lawson Daku, Latévi Max, and Canton, Sophie E. Resolving the Ultrafast Changes of Chemically Inequivalent Metal–Ligand Bonds in Photoexcited Molecular Complexes with Transient X-ray Absorption Spectroscopy. United States: N. p., 2019. Web. doi:10.1021/acsomega.8b03688.
Zhang, Jianxin, Zhang, Xiaoyi, Suarez-Alcantara, Karina, Jennings, Guy, Kurtz, Charles A., Lawson Daku, Latévi Max, & Canton, Sophie E. Resolving the Ultrafast Changes of Chemically Inequivalent Metal–Ligand Bonds in Photoexcited Molecular Complexes with Transient X-ray Absorption Spectroscopy. United States. doi:10.1021/acsomega.8b03688.
Zhang, Jianxin, Zhang, Xiaoyi, Suarez-Alcantara, Karina, Jennings, Guy, Kurtz, Charles A., Lawson Daku, Latévi Max, and Canton, Sophie E. Fri . "Resolving the Ultrafast Changes of Chemically Inequivalent Metal–Ligand Bonds in Photoexcited Molecular Complexes with Transient X-ray Absorption Spectroscopy". United States. doi:10.1021/acsomega.8b03688. https://www.osti.gov/servlets/purl/1532536.
@article{osti_1532536,
title = {Resolving the Ultrafast Changes of Chemically Inequivalent Metal–Ligand Bonds in Photoexcited Molecular Complexes with Transient X-ray Absorption Spectroscopy},
author = {Zhang, Jianxin and Zhang, Xiaoyi and Suarez-Alcantara, Karina and Jennings, Guy and Kurtz, Charles A. and Lawson Daku, Latévi Max and Canton, Sophie E.},
abstractNote = {Photoactive transition-metal complexes that incorporate heteroleptic ligands present a fast coordination shell, which is asymmetric. While it is generally expected that the metal-ligand bond lengths respond differently to photoexcitation, resolving these fine structural changes remains experimentally challenging, especially for flexible multidentate ligands. Here, ultrafast X-ray absorption spectroscopy is employed to capture directly the asymmetric elongations of chemically inequivalent metal-ligand bonds in the photoexcited spin-switching Fe-II complex [Fe-II(tpen)](2+) solvated in acetonitrile, where tpen denotes N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethylenediamine. The possibility to correlate precisely the nature of the donor/acceptor coordinating atoms to specific photoinduced structural changes within a binding motif will provide advanced diagnostics for optimizing numerous photoactive chemical and biological building blocks.},
doi = {10.1021/acsomega.8b03688},
journal = {ACS Omega},
number = 4,
volume = 4,
place = {United States},
year = {2019},
month = {4}
}

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