Photoactive transition-metal complexes that incorporate heteroleptic ligands present a first coordination shell, which is asymmetric. Although 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. In this work, 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 complex [Fe(tpen)] solvated in acetonitrile, where tpen denotes ,,','-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.

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC6648759PMC
http://dx.doi.org/10.1021/acsomega.8b03688DOI Listing

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