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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

Abstract

We report the preparation and new insight into photophysical properties of luminescent hydroxypyridonate complexes [M IIIL] - (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 Eu III and Sm III 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.

Authors:
 [1];  [1];  [2];  [1];  [1];  [2];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Stanford Univ., CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1179747
Alternate Identifier(s):
OSTI ID: 1257356
Grant/Contract Number:
AC02-05CH11231; CHE-0233882; CHE-0840505; CHE-1360046; HL069832; S10-RR027172
Resource Type:
Journal Article: Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 137; Journal Issue: 8; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Daumann, Lena J., Tatum, David S., Snyder, Benjamin E. R., Ni, Chengbao, Law, Ga-lai, Solomon, Edward I., and Raymond, Kenneth N.. New Insights into Structure and Luminescence of EuIII and SmIII Complexes of the 3,4,3-LI(1,2-HOPO) Ligand. United States: N. p., 2015. Web. doi:10.1021/ja5116524.
Daumann, Lena J., Tatum, David S., Snyder, Benjamin E. R., Ni, Chengbao, Law, Ga-lai, Solomon, Edward I., & Raymond, Kenneth N.. New Insights into Structure and Luminescence of EuIII and SmIII Complexes of the 3,4,3-LI(1,2-HOPO) Ligand. United States. doi:10.1021/ja5116524.
Daumann, Lena J., Tatum, David S., Snyder, Benjamin E. R., Ni, Chengbao, Law, Ga-lai, Solomon, Edward I., and Raymond, Kenneth N.. Wed . "New Insights into Structure and Luminescence of EuIII and SmIII Complexes of the 3,4,3-LI(1,2-HOPO) Ligand". United States. doi:10.1021/ja5116524.
@article{osti_1179747,
title = {New Insights into Structure and Luminescence of EuIII and SmIII Complexes of the 3,4,3-LI(1,2-HOPO) Ligand},
author = {Daumann, Lena J. and Tatum, David S. and Snyder, Benjamin E. R. and Ni, Chengbao and Law, Ga-lai and Solomon, Edward I. and Raymond, Kenneth N.},
abstractNote = {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.},
doi = {10.1021/ja5116524},
journal = {Journal of the American Chemical Society},
number = 8,
volume = 137,
place = {United States},
year = {Wed Jan 21 00:00:00 EST 2015},
month = {Wed Jan 21 00:00:00 EST 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/ja5116524

Citation Metrics:
Cited by: 24 works
Citation information provided by
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