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Issue 24, 2020
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Influence of thermally induced structural transformations on the magnetic and luminescence properties of tartrate-based chiral lanthanide organic-frameworks

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Abstract

This work reports on the synthesis and characterization of five enantiomeric pairs of isostructural 3D metal–organic frameworks (MOFs) with the general formula {[Ln24-tar)2(μ-tar)(H2O)2xH2O}n [where Ln(III) = Tb (Tb-L and Tb-D), Dy (Dy-L and Dy-D), Ho (Ho-L and Ho-D), Er (Er-L and Er-D) and Tm (Tm-L and Tm-D); tar = tartrate (D- or L-) and x = 3 or 4 depending on the counterpart], which possess interesting luminescence and magnetic properties. These MOFs undergo progressive and reversible dehydration processes upon controlled heating yielding three crystalline phases (Ln-L′, Ln-L′′ and Ln-L′′′). Alternating current magnetic measurements on Tb, Dy and Er-based compounds exhibit field induced single-molecule magnet behavior dominated by QTM, which is partially suppressed when diluted on a Y-based matrix. Tartrate ligands show poor room temperature sensitization of Tb and Dy centers that is enhanced at low temperature (10 K), even enabling weak Tm-based emission. More interestingly, the dehydration modulates both magnetic and photoluminescence properties on the basis of both the distortions occurring in the coordination shells and a decrease of water molecules acting as quenchers, respectively, endowing these materials with potential humidity sensing capacity. Remarkably, the Tb-based MOF shows circularly polarized luminescence (CPL), being one of the examples of this very scarce family of CPL emitters reported so far.

Graphical abstract: Influence of thermally induced structural transformations on the magnetic and luminescence properties of tartrate-based chiral lanthanide organic-frameworks

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Article information


Submitted
12 Feb 2020
Accepted
03 May 2020
First published
04 May 2020

J. Mater. Chem. C, 2020,8, 8243-8256
Article type
Paper

Influence of thermally induced structural transformations on the magnetic and luminescence properties of tartrate-based chiral lanthanide organic-frameworks

U. Huizi-Rayo, A. Zabala-Lekuona, A. Terenzi, C. M. Cruz, J. M. Cuerva, A. Rodríguez-Diéguez, J. A. García, J. M. Seco, E. San Sebastian and J. Cepeda, J. Mater. Chem. C, 2020, 8, 8243
DOI: 10.1039/D0TC00736F

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