Fluoride-Bridged {GdIII3MIII2} (M=Cr, Fe, Ga) Molecular Magnetic Refrigerants

Kasper Steen Pedersen, Giulia Lorusso, Juan José Morales, Thomas Weyhermüller, Stergios Piligkos, Saurabh Kumar Singh, Dennis Larsen, Magnus Schau-Magnussen, Gopalan Rajaraman, Marco Evangelisti, Jesper Bendix

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

The reaction of fac‐[MIIIF3(Me3tacn)]⋅x H2O with Gd(NO3)3⋅5H2O affords a series of fluoride‐bridged, trigonal bipyramidal {GdIII3MIII2} (M=Cr (1), Fe (2), Ga (3)) complexes without signs of concomitant GdF3 formation, thereby demonstrating the applicability even of labile fluoride‐complexes as precursors for 3d–4f systems. Molecular geometry enforces weak exchange interactions, which is rationalized computationally. This, in conjunction with a lightweight ligand sphere, gives rise to large magnetic entropy changes of 38.3 J kg−1 K−1 (1) and 33.1 J kg−1 K−1 (2) for the field change 7 T→0 T. Interestingly, the entropy change, and the magnetocaloric effect, are smaller in 2 than in 1 despite the larger spin ground state of the former secured by intramolecular Fe–Gd ferromagnetic interactions. This observation underlines the necessity of controlling not only the ground state but also close‐lying excited states for successful design of molecular refrigerants.
Original languageEnglish
JournalAngewandte Chemie
Volume126
Issue number9
Pages (from-to)2426-2429
ISSN0044-8249
DOIs
Publication statusPublished - 2014
Externally publishedYes

Cite this

Pedersen, K. S., Lorusso, G., Morales, J. J., Weyhermüller, T., Piligkos, S., Singh, S. K., ... Bendix, J. (2014). Fluoride-Bridged {GdIII3MIII2} (M=Cr, Fe, Ga) Molecular Magnetic Refrigerants. Angewandte Chemie, 126(9), 2426-2429. https://doi.org/10.1002/ange.201308240
Pedersen, Kasper Steen ; Lorusso, Giulia ; Morales, Juan José ; Weyhermüller, Thomas ; Piligkos, Stergios ; Singh, Saurabh Kumar ; Larsen, Dennis ; Schau-Magnussen, Magnus ; Rajaraman, Gopalan ; Evangelisti, Marco ; Bendix, Jesper. / Fluoride-Bridged {GdIII3MIII2} (M=Cr, Fe, Ga) Molecular Magnetic Refrigerants. In: Angewandte Chemie. 2014 ; Vol. 126, No. 9. pp. 2426-2429.
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title = "Fluoride-Bridged {GdIII3MIII2} (M=Cr, Fe, Ga) Molecular Magnetic Refrigerants",
abstract = "The reaction of fac‐[MIIIF3(Me3tacn)]⋅x H2O with Gd(NO3)3⋅5H2O affords a series of fluoride‐bridged, trigonal bipyramidal {GdIII3MIII2} (M=Cr (1), Fe (2), Ga (3)) complexes without signs of concomitant GdF3 formation, thereby demonstrating the applicability even of labile fluoride‐complexes as precursors for 3d–4f systems. Molecular geometry enforces weak exchange interactions, which is rationalized computationally. This, in conjunction with a lightweight ligand sphere, gives rise to large magnetic entropy changes of 38.3 J kg−1 K−1 (1) and 33.1 J kg−1 K−1 (2) for the field change 7 T→0 T. Interestingly, the entropy change, and the magnetocaloric effect, are smaller in 2 than in 1 despite the larger spin ground state of the former secured by intramolecular Fe–Gd ferromagnetic interactions. This observation underlines the necessity of controlling not only the ground state but also close‐lying excited states for successful design of molecular refrigerants.",
author = "Pedersen, {Kasper Steen} and Giulia Lorusso and Morales, {Juan Jos{\'e}} and Thomas Weyherm{\"u}ller and Stergios Piligkos and Singh, {Saurabh Kumar} and Dennis Larsen and Magnus Schau-Magnussen and Gopalan Rajaraman and Marco Evangelisti and Jesper Bendix",
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Pedersen, KS, Lorusso, G, Morales, JJ, Weyhermüller, T, Piligkos, S, Singh, SK, Larsen, D, Schau-Magnussen, M, Rajaraman, G, Evangelisti, M & Bendix, J 2014, 'Fluoride-Bridged {GdIII3MIII2} (M=Cr, Fe, Ga) Molecular Magnetic Refrigerants', Angewandte Chemie, vol. 126, no. 9, pp. 2426-2429. https://doi.org/10.1002/ange.201308240

Fluoride-Bridged {GdIII3MIII2} (M=Cr, Fe, Ga) Molecular Magnetic Refrigerants. / Pedersen, Kasper Steen; Lorusso, Giulia; Morales, Juan José; Weyhermüller, Thomas; Piligkos, Stergios; Singh, Saurabh Kumar; Larsen, Dennis; Schau-Magnussen, Magnus; Rajaraman, Gopalan; Evangelisti, Marco; Bendix, Jesper.

In: Angewandte Chemie, Vol. 126, No. 9, 2014, p. 2426-2429.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Fluoride-Bridged {GdIII3MIII2} (M=Cr, Fe, Ga) Molecular Magnetic Refrigerants

AU - Pedersen, Kasper Steen

AU - Lorusso, Giulia

AU - Morales, Juan José

AU - Weyhermüller, Thomas

AU - Piligkos, Stergios

AU - Singh, Saurabh Kumar

AU - Larsen, Dennis

AU - Schau-Magnussen, Magnus

AU - Rajaraman, Gopalan

AU - Evangelisti, Marco

AU - Bendix, Jesper

PY - 2014

Y1 - 2014

N2 - The reaction of fac‐[MIIIF3(Me3tacn)]⋅x H2O with Gd(NO3)3⋅5H2O affords a series of fluoride‐bridged, trigonal bipyramidal {GdIII3MIII2} (M=Cr (1), Fe (2), Ga (3)) complexes without signs of concomitant GdF3 formation, thereby demonstrating the applicability even of labile fluoride‐complexes as precursors for 3d–4f systems. Molecular geometry enforces weak exchange interactions, which is rationalized computationally. This, in conjunction with a lightweight ligand sphere, gives rise to large magnetic entropy changes of 38.3 J kg−1 K−1 (1) and 33.1 J kg−1 K−1 (2) for the field change 7 T→0 T. Interestingly, the entropy change, and the magnetocaloric effect, are smaller in 2 than in 1 despite the larger spin ground state of the former secured by intramolecular Fe–Gd ferromagnetic interactions. This observation underlines the necessity of controlling not only the ground state but also close‐lying excited states for successful design of molecular refrigerants.

AB - The reaction of fac‐[MIIIF3(Me3tacn)]⋅x H2O with Gd(NO3)3⋅5H2O affords a series of fluoride‐bridged, trigonal bipyramidal {GdIII3MIII2} (M=Cr (1), Fe (2), Ga (3)) complexes without signs of concomitant GdF3 formation, thereby demonstrating the applicability even of labile fluoride‐complexes as precursors for 3d–4f systems. Molecular geometry enforces weak exchange interactions, which is rationalized computationally. This, in conjunction with a lightweight ligand sphere, gives rise to large magnetic entropy changes of 38.3 J kg−1 K−1 (1) and 33.1 J kg−1 K−1 (2) for the field change 7 T→0 T. Interestingly, the entropy change, and the magnetocaloric effect, are smaller in 2 than in 1 despite the larger spin ground state of the former secured by intramolecular Fe–Gd ferromagnetic interactions. This observation underlines the necessity of controlling not only the ground state but also close‐lying excited states for successful design of molecular refrigerants.

U2 - 10.1002/ange.201308240

DO - 10.1002/ange.201308240

M3 - Journal article

VL - 126

SP - 2426

EP - 2429

JO - Angewandte Chemie

JF - Angewandte Chemie

SN - 0044-8249

IS - 9

ER -

Pedersen KS, Lorusso G, Morales JJ, Weyhermüller T, Piligkos S, Singh SK et al. Fluoride-Bridged {GdIII3MIII2} (M=Cr, Fe, Ga) Molecular Magnetic Refrigerants. Angewandte Chemie. 2014;126(9):2426-2429. https://doi.org/10.1002/ange.201308240