Direct Observation of 4f Intrashell Excitation in Luminescent Eu Complexes by Time-Resolved X‑ray Absorption Near Edge Spectroscopy

We report time-resolved X-ray absorption near edge structure (TR-XANES) measurements at the Eu L 3 edge upon photoexcitation of several EuIII-based luminescent lanthanide complexes. We find an unambiguous signature of the 4f intrashell excitation that occurs upon energy transfer from the photoactive...

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Published in:Journal of the American Chemical Society 2014-03, Vol.136 (11), p.4186-4191
Main Authors: Pacold, Joseph I, Tatum, David S, Seidler, Gerald T, Raymond, Kenneth N, Zhang, Xiaoyi, Stickrath, Andrew B, Mortensen, Devon R
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container_issue 11
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container_title Journal of the American Chemical Society
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creator Pacold, Joseph I
Tatum, David S
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Mortensen, Devon R
description We report time-resolved X-ray absorption near edge structure (TR-XANES) measurements at the Eu L 3 edge upon photoexcitation of several EuIII-based luminescent lanthanide complexes. We find an unambiguous signature of the 4f intrashell excitation that occurs upon energy transfer from the photoactive organic antennas to the lanthanide species. Phenomenologically, this observation provides the basis for direct investigation of a crucial step in the energy transfer pathways that lead to sensitized luminescence in lanthanide-based dyes. Interestingly, the details of the TR-XANES feature suggest that the degree of 4f–5d hybridization may itself vary depending on the excited state of the EuIII ion.
doi_str_mv 10.1021/ja407924m
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title Direct Observation of 4f Intrashell Excitation in Luminescent Eu Complexes by Time-Resolved X‑ray Absorption Near Edge Spectroscopy
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