Multifunctional self-refrigerated multivariate {GdLn} (Ln = Dy, Tb, Tb/Eu) metal-organic frameworks

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...

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Detalhes bibliográficos
Autores: Li, Zhen|||0000-0002-8497-7497, Arauzo, Ana|||0000-0002-5999-341X, Roscini, Claudio|||0000-0002-0157-8934, Giner Planas, José|||0000-0002-1648-2169, Bartolome, Elena|||0000-0001-5108-0977
Tipo de documento: artigo
Data de publicação:2024
País:España
Recursos:Universitat Autònoma de Barcelona
Repositório:Dipòsit Digital de Documents de la UAB
Idioma:inglês
OAI Identifier:oai:ddd.uab.cat:302502
Acesso em linha:https://ddd.uab.cat/record/302502
https://dx.doi.org/urn:doi:10.1039/d4ta03835e
Access Level:Acceso aberto
Descrição
Resumo: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.