Toward Opto-Structural Correlation to Investigate Luminescence Thermometry in an Organometallic Eu(II) Complex

Roberto M. Diaz-Rodriguez; Diogo A. Gálico; Daniel Chartrand; Elizaveta A. Suturina; Muralee Murugesu

doi:10.1021/jacs.1c11076

Toward Opto-Structural Correlation to Investigate Luminescence Thermometry in an Organometallic Eu(II) Complex

Roberto M. Diaz-Rodriguez, Diogo A. Gálico, Daniel Chartrand, Elizaveta A. Suturina, Muralee Murugesu

Department of Chemistry

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Abstract

Lanthanide-based luminescent materials have unique properties and are well-studied for many potential applications. In particular, the characteristic 5d → 4f emission of divalent lanthanide ions such as Eu^II allows for tunability of the emissive properties via modulation of the coordination environment. We report the synthesis and photoluminescence investigation of pentamethylcyclopentadienyleuropium(II) tetrahydroborate bis(tetrahydrofuran) dimer (1), the first example of an organometallic, discrete molecular Eu^II band-shift luminescence thermometer. Complex 1 exhibits an absolute sensitivity of 8.2 cm^–1 K^–1 at 320 K, the highest thus far observed for a lanthanide-based band-shift thermometer. Opto-structural correlation via variable-temperature single-crystal X-ray diffraction and fluorescence spectroscopy allows rationalization of the remarkable thermometric luminescence of complex 1 and reveals the significant potential of molecular Eu^II compounds in luminescence thermometry.

Original language	English
Pages (from-to)	912-921
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	144
Issue number	2
Early online date	6 Jan 2022
DOIs	https://doi.org/10.1021/jacs.1c11076
Publication status	Published - 19 Jan 2022

Funding

We thank the Canadian Foundation for Innovation (CFI) and the Natural Sciences and Engineering Research Council of Canada (NSERC) for financial support of this work. We thank Dr. Jeffrey Ovens and the uOttawa X-ray Core Facility, as well as the X-ray Diffraction Laboratory at the Université de Montréal, for access to crystallographic instrumentation and resources. We are thankful to Dr. A. A. Kitos (Murugesu Group) for useful discussions regarding crystallographic refinement.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.1c11076

LumTherm Manuscript (accepted author manuscript)
This document is the Accepted Manuscript version of a Published Work that appeared in final form in J. Am. Chem. Soc, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.1c11076
Accepted author manuscript, 2 MB

Cite this

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abstract = "Lanthanide-based luminescent materials have unique properties and are well-studied for many potential applications. In particular, the characteristic 5d → 4f emission of divalent lanthanide ions such as EuII allows for tunability of the emissive properties via modulation of the coordination environment. We report the synthesis and photoluminescence investigation of pentamethylcyclopentadienyleuropium(II) tetrahydroborate bis(tetrahydrofuran) dimer (1), the first example of an organometallic, discrete molecular EuII band-shift luminescence thermometer. Complex 1 exhibits an absolute sensitivity of 8.2 cm–1 K–1 at 320 K, the highest thus far observed for a lanthanide-based band-shift thermometer. Opto-structural correlation via variable-temperature single-crystal X-ray diffraction and fluorescence spectroscopy allows rationalization of the remarkable thermometric luminescence of complex 1 and reveals the significant potential of molecular EuII compounds in luminescence thermometry.",

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AU - Gálico, Diogo A.

AU - Chartrand, Daniel

AU - Suturina, Elizaveta A.

AU - Murugesu, Muralee

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AB - Lanthanide-based luminescent materials have unique properties and are well-studied for many potential applications. In particular, the characteristic 5d → 4f emission of divalent lanthanide ions such as EuII allows for tunability of the emissive properties via modulation of the coordination environment. We report the synthesis and photoluminescence investigation of pentamethylcyclopentadienyleuropium(II) tetrahydroborate bis(tetrahydrofuran) dimer (1), the first example of an organometallic, discrete molecular EuII band-shift luminescence thermometer. Complex 1 exhibits an absolute sensitivity of 8.2 cm–1 K–1 at 320 K, the highest thus far observed for a lanthanide-based band-shift thermometer. Opto-structural correlation via variable-temperature single-crystal X-ray diffraction and fluorescence spectroscopy allows rationalization of the remarkable thermometric luminescence of complex 1 and reveals the significant potential of molecular EuII compounds in luminescence thermometry.

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Toward Opto-Structural Correlation to Investigate Luminescence Thermometry in an Organometallic Eu(II) Complex

Abstract

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