Multifunctional self-refrigerated multivariate {GdLn} (Ln = Dy, Tb, Tb/Eu) metal-organic frameworks
Li, Zhen (Institut de Ciència de Materials de Barcelona)
Arauzo, Ana (Universidad de Zaragoza)
Roscini, Claudio (Institut Català de Nanociència i Nanotecnologia)
Giner Planas, José (Institut de Ciència de Materials de Barcelona)
Bartolome, Elena (Institut de Ciència de Materials de Barcelona)

Date:	2024
Abstract:	Multivariate metal-organic frameworks (MOFs) containing multiple lanthanide ions present a compelling avenue for developing versatile materials with tailored properties. In this work, we synthesized "self-refrigerated" multifunctional carborane-based MOFs of formula unit {[(GdLn)(mCB-L)(NO)(DMF)]·Solv} strategically combining Gd ions, known for their ability to achieve large magnetocaloric effects (MCE), with various lanthanides (Ln = Dy, Tb, Eu, Tb/Eu) intended to act as Single Molecule Magnet (SMM) or/and luminescent units. The intricate magnetic, thermal, and optical properties of these multivariate Ln-MOFs were unraveled through a comprehensive characterization employing dc and ac magnetometry, X-ray Absorption Spectroscopy (XAS), X-ray Magnetic Circular Dichroism (XMCD), and luminescence measurements. Element-selective XAS-XMCD technique proved instrumental in elucidating the magnetic properties of the individual lanthanides, and their contribution to the macroscopic properties of the MOFs. We demonstrate that GdLn (Ln = Tb, Dy) MOFs exhibit multifunctionality, incorporating MCE, field-induced magnetic relaxation dominated by the anisotropic ion, and green emission for Ln = Tb. Conversely, GdLn (Ln = Eu, Eu/Tb) MOFs display MCE, field-induced SMM behavior associated with Gd, and red/yellow luminescent emission for Ln = Eu and Eu/Tb substitutions, respectively. Our findings significantly contribute to our understanding of "complex magnetic molecular materials" and set a pathway for the design of multifunctional multi-lanthanide MOFs endowed with tailored properties for various technological applications.
Grants:	Agencia Estatal de Investigación PID2022-138492NB-I00 Agencia Estatal de Investigación PID2022-136892NB-I00 Agència de Gestió d'Ajuts Universitaris i de Recerca 2021/SGR-00442 Agencia Estatal de Investigación CEX2023-001263-S
Rights:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, sempre que no sigui amb finalitats comercials, i sempre que es reconegui l'autoria de l'obra original.
Language:	Anglès
Document:	Article ; recerca ; Versió publicada
Published in:	Journal of materials chemistry. A, Vol. 12, Issue 33 (July 2024) , p. 21971-21986, ISSN 2050-7496

DOI: 10.1039/d4ta03835e

16 p, 3.8 MB

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Research literature > UAB research groups literature > Research Centres and Groups (research output) > Experimental sciences > Catalan Institute of Nanoscience and Nanotechnology (ICN2)
Articles > Research articles
Articles > Published articles