Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb)

Jeffrey D. Einkauf; Tanya T. Kelley; Benny C. Chan; Daniel T. De Lill

doi:10.1021/acs.inorgchem.6b00878

Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C₁₅H₉O₅)₃(H₂O)₃]_n (Ln = Eu, Tb)

Jeffrey D. Einkauf, Tanya T. Kelley, Benny C. Chan, Daniel T. De Lill

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

42 Scopus citations

Abstract

A coordination polymer [Ln(C₁₅H₉O₉)₃(H₂O)₃]_n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C₁₅H₉O₉)₃(D₂O)₃) and dehydrated (Ln(C₁₅H₉O₉)₃) analogues were also studied. When bound H₂O was replaced by D₂O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.

Original language	English
Pages (from-to)	7920-7927
Number of pages	8
Journal	Inorganic Chemistry
Volume	55
Issue number	16
DOIs	https://doi.org/10.1021/acs.inorgchem.6b00878
State	Published - Aug 15 2016
Externally published	Yes

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10.1021/acs.inorgchem.6b00878

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@article{c08ae40bfa5d4f6f989c9ca3e31752d1,

title = "Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb)",

abstract = "A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.",

author = "Einkauf, {Jeffrey D.} and Kelley, {Tanya T.} and Chan, {Benny C.} and {De Lill}, {Daniel T.}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = aug,

day = "15",

doi = "10.1021/acs.inorgchem.6b00878",

language = "English",

volume = "55",

pages = "7920--7927",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "16",

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Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C₁₅H₉O₅)₃(H₂O)₃]_n (Ln = Eu, Tb). / Einkauf, Jeffrey D.; Kelley, Tanya T.; Chan, Benny C. et al.
In: Inorganic Chemistry, Vol. 55, No. 16, 15.08.2016, p. 7920-7927.

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

TY - JOUR

T1 - Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs

T2 - Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb)

AU - Einkauf, Jeffrey D.

AU - Kelley, Tanya T.

AU - Chan, Benny C.

AU - De Lill, Daniel T.

PY - 2016/8/15

Y1 - 2016/8/15

N2 - A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.

AB - A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.

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SN - 0020-1669

VL - 55

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JO - Inorganic Chemistry

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Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C₁₅H₉O₅)₃(H₂O)₃]_n (Ln = Eu, Tb)

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