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Title: New Insights into Structure and Luminescence of Eu III and Sm III Complexes of the 3,4,3-LI(1,2-HOPO) Ligand

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/ja5116524· OSTI ID:1179747
 [1];  [1];  [2];  [1];  [1];  [2];  [1]
  1. Chemical Science Division, Lawrence Berkeley National Laboratory, and Department of Chemistry, University of California, Berkeley, California 94720, United States
  2. Department of Chemistry, Stanford University, Stanford, California 94305, United States

We report the preparation and new insight into photophysical properties of luminescent hydroxypyridonate complexes [MIIIL]- (M = Eu or Sm) of the versatile 3,4,3-LI(1,2-HOPO) ligand (L). We report the crystal structure of this ligand with EuIII as well as insights into the coordination behavior and geometry in solution by using magnetic circular dichroism. In addition TD-DFT calculations were used to examine the excited states of the two different chromophores present in the 3,4,3-LI(1,2-HOPO) ligand. We find that the EuIII and SmIII complexes of this ligand undergo a transformation after in situ preparation to yield complexes with higher quantum yield (QY) over time. We propose that the lower QY in the in situ complexes is not only due to water quenching but could also be due to a lower degree of f-orbital overlap (in a kinetic isomer) as indicated by magnetic circular dichroism measurements.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-05CH11231; CHE-0233882; CHE-0840505; CHE-1360046; HL069832; S10-RR027172
OSTI ID:
1179747
Alternate ID(s):
OSTI ID: 1257356
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 137 Journal Issue: 8; ISSN 0002-7863
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 58 works
Citation information provided by
Web of Science

Figures / Tables (5)