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

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• 作者：Joseph I. Pacold ; David S. Tatum ; Gerald T. Seidler ; Kenneth N. Raymond ; Xiaoyi Zhang ; Andrew B. Stickrath ; Devon R. Mortensen
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：March 19, 2014
• 年：2014
• 卷：136
• 期：11
• 页码：4186-4191
• 全文大小：389K
• 年卷期：v.136,no.11(March 19, 2014)
• ISSN：1520-5126

文摘

We report time-resolved X-ray absorption near edge structure (TR-XANES) measurements at the Eu L₃ edge upon photoexcitation of several Eu^III-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鈥?d hybridization may itself vary depending on the excited state of the Eu^III ion.