Azido- and amino-substituted dipicolinates for the sensitization of the luminescent lanthanides EuIII and TbIII

Katherine R. Johnson; Ana de Bettencourt-Dias

doi:10.1016/j.ica.2020.120003

Azido- and amino-substituted dipicolinates for the sensitization of the luminescent lanthanides Eu^III and Tb^III

Katherine R. Johnson, Ana de Bettencourt-Dias

University of Nevada, Reno

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

Dipicolinate-based ligands substituted with azido- or amino- functional groups were synthesized and characterized. Crystal structures of E_N3, C_N3, C_NH2, and E_NH2 were obtained, and the ability of these compounds to sensitize Ln^III luminescence (Ln^III = Eu^III and Tb^III) was explored. Luminescence efficiencies of Eu^III and Tb^III were determined and are ϕ_Eu = 0.11%, 0.15%, and 13.8% for [Ln(C_N3)₃]³⁺, [Ln(E_N3)₃]³⁺, [Ln(C_NH2)₃]³⁺, respectively, and ϕ^Tb = 0.30%, 0.27%, and 28.9% for [Ln(C_N3)₃]³⁺, [Ln(E_N3)₃]³⁺, [Ln(E_NH2)₃]³⁺. The highest luminescence efficiencies are ϕ_Eu = 14.4% for [Eu(E_NH2)₃]³⁺ and ϕ_Tb = 29.7% for [Tb(C_NH2)₃]³⁺. Similar ¹S and ³T excited state energies were observed for all ligands and did not explain the observed discrepancies in luminescence efficiency of their Tb^III and Eu^III complexes. Further analysis revealed that the azido-derivatives were not photostable, which likely contributed to the low luminescence efficiency.

Original language	English
Article number	120003
Journal	Inorganica Chimica Acta
Volume	514
DOIs	https://doi.org/10.1016/j.ica.2020.120003
State	Published - Jan 1 2021
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2020 Elsevier B.V.

Keywords

Amido-substituted dipicolinato
Azido-substituted dipicolinato
Lanthanide complexes
Luminescence
X-ray crystallography

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10.1016/j.ica.2020.120003

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title = "Azido- and amino-substituted dipicolinates for the sensitization of the luminescent lanthanides EuIII and TbIII",

abstract = "Dipicolinate-based ligands substituted with azido- or amino- functional groups were synthesized and characterized. Crystal structures of EN3, CN3, CNH2, and ENH2 were obtained, and the ability of these compounds to sensitize LnIII luminescence (LnIII = EuIII and TbIII) was explored. Luminescence efficiencies of EuIII and TbIII were determined and are ϕEu = 0.11%, 0.15%, and 13.8% for [Ln(CN3)3]3+, [Ln(EN3)3]3+, [Ln(CNH2)3]3+, respectively, and ϕTb = 0.30%, 0.27%, and 28.9% for [Ln(CN3)3]3+, [Ln(EN3)3]3+, [Ln(ENH2)3]3+. The highest luminescence efficiencies are ϕEu = 14.4% for [Eu(ENH2)3]3+ and ϕTb = 29.7% for [Tb(CNH2)3]3+. Similar 1S and 3T excited state energies were observed for all ligands and did not explain the observed discrepancies in luminescence efficiency of their TbIII and EuIII complexes. Further analysis revealed that the azido-derivatives were not photostable, which likely contributed to the low luminescence efficiency.",

keywords = "Amido-substituted dipicolinato, Azido-substituted dipicolinato, Lanthanide complexes, Luminescence, X-ray crystallography",

author = "Johnson, {Katherine R.} and {de Bettencourt-Dias}, Ana",

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year = "2021",

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doi = "10.1016/j.ica.2020.120003",

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T1 - Azido- and amino-substituted dipicolinates for the sensitization of the luminescent lanthanides EuIII and TbIII

AU - Johnson, Katherine R.

AU - de Bettencourt-Dias, Ana

PY - 2021/1/1

Y1 - 2021/1/1

N2 - Dipicolinate-based ligands substituted with azido- or amino- functional groups were synthesized and characterized. Crystal structures of EN3, CN3, CNH2, and ENH2 were obtained, and the ability of these compounds to sensitize LnIII luminescence (LnIII = EuIII and TbIII) was explored. Luminescence efficiencies of EuIII and TbIII were determined and are ϕEu = 0.11%, 0.15%, and 13.8% for [Ln(CN3)3]3+, [Ln(EN3)3]3+, [Ln(CNH2)3]3+, respectively, and ϕTb = 0.30%, 0.27%, and 28.9% for [Ln(CN3)3]3+, [Ln(EN3)3]3+, [Ln(ENH2)3]3+. The highest luminescence efficiencies are ϕEu = 14.4% for [Eu(ENH2)3]3+ and ϕTb = 29.7% for [Tb(CNH2)3]3+. Similar 1S and 3T excited state energies were observed for all ligands and did not explain the observed discrepancies in luminescence efficiency of their TbIII and EuIII complexes. Further analysis revealed that the azido-derivatives were not photostable, which likely contributed to the low luminescence efficiency.

AB - Dipicolinate-based ligands substituted with azido- or amino- functional groups were synthesized and characterized. Crystal structures of EN3, CN3, CNH2, and ENH2 were obtained, and the ability of these compounds to sensitize LnIII luminescence (LnIII = EuIII and TbIII) was explored. Luminescence efficiencies of EuIII and TbIII were determined and are ϕEu = 0.11%, 0.15%, and 13.8% for [Ln(CN3)3]3+, [Ln(EN3)3]3+, [Ln(CNH2)3]3+, respectively, and ϕTb = 0.30%, 0.27%, and 28.9% for [Ln(CN3)3]3+, [Ln(EN3)3]3+, [Ln(ENH2)3]3+. The highest luminescence efficiencies are ϕEu = 14.4% for [Eu(ENH2)3]3+ and ϕTb = 29.7% for [Tb(CNH2)3]3+. Similar 1S and 3T excited state energies were observed for all ligands and did not explain the observed discrepancies in luminescence efficiency of their TbIII and EuIII complexes. Further analysis revealed that the azido-derivatives were not photostable, which likely contributed to the low luminescence efficiency.

KW - Amido-substituted dipicolinato

KW - Azido-substituted dipicolinato

KW - Lanthanide complexes

KW - Luminescence

KW - X-ray crystallography

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