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

Daumann, Lena J.; Tatum, David S.; Snyder, Benjamin E. R.; Ni, Chengbao; Law, Ga-lai; Solomon, Edward I.; Raymond, Kenneth N.

doi:10.1021/ja5116524

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:

Daumann, Lena J. ^[1]; Tatum, David S. ^[1]; Snyder, Benjamin E. R. ^[2]; Ni, Chengbao ^[1]; Law, Ga-lai ^[1]; Solomon, Edward I. ^[2]; Raymond, Kenneth N. ^[1]

Chemical Science Division, Lawrence Berkeley National Laboratory, and Department of Chemistry, University of California, Berkeley, California 94720, United States
Department of Chemistry, Stanford University, Stanford, California 94305, United States

Publication Date:: Thu Feb 19 00:00:00 EST 2015

Research Org.:: Lawrence Berkeley National Laboratory (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:: 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.

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                    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.  https://doi.org/10.1021/ja5116524

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                    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.  https://doi.org/10.1021/ja5116524.

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@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},

  number       = 8,

  volume       = 137,

  place        = {United States},

  year         = {Thu Feb 19 00:00:00 EST 2015},

  month        = {Thu Feb 19 00:00:00 EST 2015}

}

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Figures / Tables:

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

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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

Citation Formats

Figures / Tables:

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