Luminescence and Single‐Molecule Magnet Properties in Ideal Symmetry Compounds: Example of a Near‐Planar Tricoordinate Ytterbium(III) Amide

Abstract We are reporting on the use of a low‐coordinate YbIII amide with near‐ideal planar trigonal [Yb{N(SiMe3)2}3] (1) and on a bipyramidal trigonal derivative [Yb{N(SiMe2H)2}3 ⋅ (thf)2] (2) that constitute quintessential cases to investigate luminescent and magnetic properties otherwise usually...

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Main Authors: Dr. Nimisha Jain, Dr. Félix Houard, Rémi Marchal, Marie Cordier, Dr. Boris Le Guennic, Dr. Yan Suffren, Dr. Yann Sarazin, Prof. Kevin Bernot
Format: Article
Language:English
Published: Wiley-VCH 2024-11-01
Series:ChemistryEurope
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Online Access:https://doi.org/10.1002/ceur.202400062
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author Dr. Nimisha Jain
Dr. Félix Houard
Rémi Marchal
Marie Cordier
Dr. Boris Le Guennic
Dr. Yan Suffren
Dr. Yann Sarazin
Prof. Kevin Bernot
author_facet Dr. Nimisha Jain
Dr. Félix Houard
Rémi Marchal
Marie Cordier
Dr. Boris Le Guennic
Dr. Yan Suffren
Dr. Yann Sarazin
Prof. Kevin Bernot
author_sort Dr. Nimisha Jain
collection DOAJ
description Abstract We are reporting on the use of a low‐coordinate YbIII amide with near‐ideal planar trigonal [Yb{N(SiMe3)2}3] (1) and on a bipyramidal trigonal derivative [Yb{N(SiMe2H)2}3 ⋅ (thf)2] (2) that constitute quintessential cases to investigate luminescent and magnetic properties otherwise usually blurred on less symmetrical compounds. These compounds represent the first experimental objects that allow for the confirmation of the recent conjecture about best‐performing SMM built on the archetypal prolate lanthanide ion. We have performed a combined theoretical, luminescent, and magnetic study on these molecules. For 1, a spectacular split of the 2F7/2 ground state of 1312 cm−1 is measured by low‐temperature near‐infra‐red luminescence as well as the calculated pure wavefunction composition of the low‐lying Kramers doublets, making this complex a textbook example of a prolate SMM. These results are corroborated by comparison with 2, that exhibits as expected a 50 % decrease of the ground state splitting compared to 1. Yet, we show that these remarkable features are insufficient to promote SMM behavior, and Orbach relaxation is unlikely to occur even on such an ideal low‐coordinate SMM without control of spin‐phonon coupling.
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spelling doaj-art-ecee32b1873f4b81a94b4e557aecc27f2025-08-20T02:14:15ZengWiley-VCHChemistryEurope2751-47652024-11-0126n/an/a10.1002/ceur.202400062Luminescence and Single‐Molecule Magnet Properties in Ideal Symmetry Compounds: Example of a Near‐Planar Tricoordinate Ytterbium(III) AmideDr. Nimisha Jain0Dr. Félix Houard1Rémi Marchal2Marie Cordier3Dr. Boris Le Guennic4Dr. Yan Suffren5Dr. Yann Sarazin6Prof. Kevin Bernot7Univ Rennes INSA Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226 Université de Rennes Rennes FRANCEUniv Rennes INSA Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226 Université de Rennes Rennes FRANCEUniv Rennes INSA Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226 Université de Rennes Rennes FRANCEUniv Rennes INSA Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226 Université de Rennes Rennes FRANCEUniv Rennes INSA Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226 Université de Rennes Rennes FRANCEUniv Rennes INSA Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226 Université de Rennes Rennes FRANCEUniv Rennes INSA Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226 Université de Rennes Rennes FRANCEUniv Rennes INSA Rennes CNRS ISCR (Institut des Sciences Chimiques de Rennes) UMR 6226 Université de Rennes Rennes FRANCEAbstract We are reporting on the use of a low‐coordinate YbIII amide with near‐ideal planar trigonal [Yb{N(SiMe3)2}3] (1) and on a bipyramidal trigonal derivative [Yb{N(SiMe2H)2}3 ⋅ (thf)2] (2) that constitute quintessential cases to investigate luminescent and magnetic properties otherwise usually blurred on less symmetrical compounds. These compounds represent the first experimental objects that allow for the confirmation of the recent conjecture about best‐performing SMM built on the archetypal prolate lanthanide ion. We have performed a combined theoretical, luminescent, and magnetic study on these molecules. For 1, a spectacular split of the 2F7/2 ground state of 1312 cm−1 is measured by low‐temperature near‐infra‐red luminescence as well as the calculated pure wavefunction composition of the low‐lying Kramers doublets, making this complex a textbook example of a prolate SMM. These results are corroborated by comparison with 2, that exhibits as expected a 50 % decrease of the ground state splitting compared to 1. Yet, we show that these remarkable features are insufficient to promote SMM behavior, and Orbach relaxation is unlikely to occur even on such an ideal low‐coordinate SMM without control of spin‐phonon coupling.https://doi.org/10.1002/ceur.202400062lanthanidesluminescenceprolatesingle-molecule magnetsytterbium(III)
spellingShingle Dr. Nimisha Jain
Dr. Félix Houard
Rémi Marchal
Marie Cordier
Dr. Boris Le Guennic
Dr. Yan Suffren
Dr. Yann Sarazin
Prof. Kevin Bernot
Luminescence and Single‐Molecule Magnet Properties in Ideal Symmetry Compounds: Example of a Near‐Planar Tricoordinate Ytterbium(III) Amide
ChemistryEurope
lanthanides
luminescence
prolate
single-molecule magnets
ytterbium(III)
title Luminescence and Single‐Molecule Magnet Properties in Ideal Symmetry Compounds: Example of a Near‐Planar Tricoordinate Ytterbium(III) Amide
title_full Luminescence and Single‐Molecule Magnet Properties in Ideal Symmetry Compounds: Example of a Near‐Planar Tricoordinate Ytterbium(III) Amide
title_fullStr Luminescence and Single‐Molecule Magnet Properties in Ideal Symmetry Compounds: Example of a Near‐Planar Tricoordinate Ytterbium(III) Amide
title_full_unstemmed Luminescence and Single‐Molecule Magnet Properties in Ideal Symmetry Compounds: Example of a Near‐Planar Tricoordinate Ytterbium(III) Amide
title_short Luminescence and Single‐Molecule Magnet Properties in Ideal Symmetry Compounds: Example of a Near‐Planar Tricoordinate Ytterbium(III) Amide
title_sort luminescence and single molecule magnet properties in ideal symmetry compounds example of a near planar tricoordinate ytterbium iii amide
topic lanthanides
luminescence
prolate
single-molecule magnets
ytterbium(III)
url https://doi.org/10.1002/ceur.202400062
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