New insights into structure and luminescence of EuIII and SmIII complexes of the 3,4,3-LI(1,2-HOPO) ligand

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

doi:10.1021/ja5116524

New insights into structure and luminescence of Eu^III and Sm^III complexes of the 3,4,3-LI(1,2-HOPO) ligand

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

Research output: Journal article publication › Journal article › Academic research › peer-review

63 Citations (Scopus)

Abstract

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. It is proposed 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.

Original language	English
Pages (from-to)	2816-2819
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	137
Issue number	8
DOIs	https://doi.org/10.1021/ja5116524
Publication status	Published - 4 Mar 2015
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja5116524

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title = "New insights into structure and luminescence of EuIII and SmIII 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 [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. It is proposed 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.",

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AU - Daumann, Lena J.

AU - Tatum, David S.

AU - Snyder, Benjamin E.R.

AU - Ni, Chengbao

AU - Law, Ga Lai

AU - Solomon, Edward I.

AU - Raymond, Kenneth N.

PY - 2015/3/4

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N2 - 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. It is proposed 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.

AB - 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. It is proposed 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.

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JF - Journal of the American Chemical Society

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ER -

New insights into structure and luminescence of Eu^III and Sm^III complexes of the 3,4,3-LI(1,2-HOPO) ligand

Abstract

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