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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. 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
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 Name: Journal of the American Chemical Society Journal Volume: 137 Journal Issue: 8; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society
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 Eu III and Sm III 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 Eu III and Sm III 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. Thu . "New Insights into Structure and Luminescence of Eu III and Sm III 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 Eu III and Sm III 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},
issn = {0002-7863},
number = 8,
volume = 137,
place = {United States},
year = {2015},
month = {2}
}

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
Web of Science

Figures / Tables:

Scheme 1. Scheme 1.: Spermine-Linked 3,4,3-LI(1,2-HOPO) Ligand for Sensitization of EuIII and SmIII (Coordinating Atoms in Red)

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Works referencing / citing this record:

Correlation of Structural and Magnetic Properties in a Set of Mononuclear Lanthanide Complexes
journal, March 2018

  • Comba, Peter; Daumann, Lena J.; Klingeler, Rüdiger
  • Chemistry - A European Journal, Vol. 24, Issue 20
  • DOI: 10.1002/chem.201704822

Structural effects on the photophysical properties of mono-β-diketonate and bis-β-diketonate Eu III complexes
journal, January 2015

  • Zhu, Tianyu; Chen, Peng; Li, Hongfeng
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 24
  • DOI: 10.1039/c5cp01392e

Ultrahigh luminescence quantum yield lanthanide coordination polymer as a multifunctional sensor
journal, January 2018

  • Zheng, Kai; Liu, Ziqi; Jiang, Yefei
  • Dalton Transactions, Vol. 47, Issue 48
  • DOI: 10.1039/c8dt03832e

Inducing selectivity and chirality in group IV metal coordination with high-denticity hydroxypyridinones
journal, January 2019

  • Deblonde, Gauthier J. -P.; Lohrey, Trevor D.; Abergel, Rebecca J.
  • Dalton Transactions, Vol. 48, Issue 23
  • DOI: 10.1039/c9dt01031a

Correlation of Structural and Magnetic Properties in a Set of Mononuclear Lanthanide Complexes
journal, March 2018

  • Comba, Peter; Daumann, Lena J.; Klingeler, Rüdiger
  • Chemistry - A European Journal, Vol. 24, Issue 20
  • DOI: 10.1002/chem.201704822

Structural effects on the photophysical properties of mono-β-diketonate and bis-β-diketonate Eu III complexes
journal, January 2015

  • Zhu, Tianyu; Chen, Peng; Li, Hongfeng
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 24
  • DOI: 10.1039/c5cp01392e

Ultrahigh luminescence quantum yield lanthanide coordination polymer as a multifunctional sensor
journal, January 2018

  • Zheng, Kai; Liu, Ziqi; Jiang, Yefei
  • Dalton Transactions, Vol. 47, Issue 48
  • DOI: 10.1039/c8dt03832e

Inducing selectivity and chirality in group IV metal coordination with high-denticity hydroxypyridinones
journal, January 2019

  • Deblonde, Gauthier J. -P.; Lohrey, Trevor D.; Abergel, Rebecca J.
  • Dalton Transactions, Vol. 48, Issue 23
  • DOI: 10.1039/c9dt01031a

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.