Title: Energy Transfer from Antenna Ligand to Europium(III) Followed Using Ultrafast Optical and X-ray Spectroscopy

Journal Article · · Journal of the American Chemical Society
ORCiD logo [1];  [2]; ORCiD logo [3];  [3]; ORCiD logo [4]; ORCiD logo [2]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States)
  4. Univ. of Queensland, Brisbane (Australia)
+ Show Author Affiliations

A series of highly luminescent europium(III) complexes which exhibit photoluminescence from the Eu(III) center following energy transfer from the UV absorbing organic sensitizer have been investigated using a combination of ultrafast optical transient absorption and Eu L3 X-ray transient absorption techniques. We have previously demon- strated that the latter can be used as a signature of 4f–4f excitation responsible for the photoluminescence in these Eu(III) coordination complexes, but the long time scale of the earlier measurements did not allow direct observation of the ligand-to-metal energy transfer step, preventing a determi- nation of the sensitization mechanism. Here, we provide the first direct experimental verification that Dexter electron exchange from the ligand triplet state is the dominant energy transfer mechanism in these photoluminescent systems. Moreover, the optical transient absorption results obtained herein imply that energy transfer for all three compounds has near unity yield, regardless of differences in the sensitization efficiencies, suggesting that the variations in the sensitization efficiencies are determined almost entirely by differences in the ligand-centered intersystem crossing rates. As a result, the implications for the rational design of more effective photoluminescent lanthanide complexes are discussed.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1559459
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 28 Vol. 141; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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