TY - JOUR
T1 - Exploiting High Order Magnetic Anisotropy for Advanced Magnetocaloric Refrigerants
AU - Tacconi, Leonardo
AU - Manvell, Anna S.
AU - Briganti, Matteo
AU - Czernia, Dominik
AU - Weihe, Høgni
AU - Konieczny, Piotr
AU - Bendix, Jesper
AU - Perfetti, Mauro
N1 - Funding Information:
This work was funded by the European Union (ERC, ELECTRA, 101039890). Views and opinions expressed are however those of the author(s) only and do not necessarily reflect those of the European Union or the European Research Council. Neither the European Union nor the granting authority can be held responsible for them. The financial support provided by the MUR\u2014Dipartimenti di Eccellenza 2023\u20132027 (DICUS 2.0) (ref. no. B96C1700020008) to the Department of Chemistry \u201CUgo Schiff\u201D of the University of Florence is acknowledged. JB acknowledges support from the Independent Research Fund Denmark (1026\u201000082B). PK acknowledges support from the National Science Centre (Poland) grant SONATA no. (2018/31/D/ST8/02118). Dr. Gemma K. Gransbury is kindly acknowledged for proofreading. Prof. K. Bernot is kindly acknowledged for scientific discussion. Open Access publishing facilitated by Universit\u00E0 degli Studi di Firenze, as part of the Wiley \u2010 CRUI\u2010CARE agreement.
Publisher Copyright:
© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.
PY - 2024
Y1 - 2024
N2 - Three new 3 d–4 f complexes of general formula trans-[MF2(py)4][LnDOTA] (M=Cr3+ or Co3+, Ln=Dy3+ or Y3+, py=pyridine and DOTA=tetraazacyclododecane-N,N′,N′′,N′′′-tetraacetate) have been synthetised. The fluoride-bridged systems were designed to achieve perfect tetragonal symmetry by combining four-fold symmetric lanthanide and transition metal building blocks. From single crystal measurements, an unprecedented switch of the tetragonal anisotropy of the Dy3+ complexes has been observed. A combination of spectroscopic observations, magnetometry measurements and ab initio calculations allowed us to pinpoint the origin of this phenomenon, which is related to the peculiar energy level structure of the complexes. Moreover, the fourfold anisotropy of the complex has been exploited to design a rotating magnetocaloric experiment showing that tetragonal anisotropy holds great potential to engineer a new class of more efficient magnetic refrigerants.
AB - Three new 3 d–4 f complexes of general formula trans-[MF2(py)4][LnDOTA] (M=Cr3+ or Co3+, Ln=Dy3+ or Y3+, py=pyridine and DOTA=tetraazacyclododecane-N,N′,N′′,N′′′-tetraacetate) have been synthetised. The fluoride-bridged systems were designed to achieve perfect tetragonal symmetry by combining four-fold symmetric lanthanide and transition metal building blocks. From single crystal measurements, an unprecedented switch of the tetragonal anisotropy of the Dy3+ complexes has been observed. A combination of spectroscopic observations, magnetometry measurements and ab initio calculations allowed us to pinpoint the origin of this phenomenon, which is related to the peculiar energy level structure of the complexes. Moreover, the fourfold anisotropy of the complex has been exploited to design a rotating magnetocaloric experiment showing that tetragonal anisotropy holds great potential to engineer a new class of more efficient magnetic refrigerants.
KW - lanthanide complexes
KW - magnetic anisotropy switch
KW - molecular magnetism
KW - rotating magnetocaloric effect
U2 - 10.1002/anie.202417582
DO - 10.1002/anie.202417582
M3 - Journal article
C2 - 39556465
AN - SCOPUS:85210361496
VL - 64
JO - Angewandte Chemie International Edition
JF - Angewandte Chemie International Edition
SN - 1433-7851
IS - 5
M1 - e202417582
ER -