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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

Journal Article · · ACS Omega

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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1532536
Journal Information:
ACS Omega, Vol. 4, Issue 4; ISSN 2470-1343
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

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Cited By (1)

Resolving structures of transition metal complex reaction intermediates with femtosecond EXAFS journal January 2020