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Issue 5, 2019
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Aggregation of [Ln III12] clusters by the dianion of 3-formylsalicylic acid. Synthesis, crystal structures, magnetic and luminescence properties

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Abstract

Three isostrucutral dodecanuclear clusters with the general formula [Ln12(fsa)12f3-OH)12(DMF)12nDMF (fsa2− is the dianion of 3-formylsalicylic acid; Ln = Eu 1, Gd 2, Dy 3) have been obtained from the reaction of fromylsalicyclic acid (H2fsa), tetrabutylammonium hydroxide and Ln(NO3)3·6H2O in methanol/DMF. Their structure consists of four vertex-sharing heterocubanes. Each heterocubane unit is assembled from four LnIII ions, three μ3-OH groups and one μ3-oxygen atom arising from the fsa2− carboxylato group. The photophysical properties of the europium derivative investigated at both 300 and 80 K sustain a relative intense emission obtained under low power LED excitation at 420 nm. The dysprosium derivative shows a SMM behavior with an effective energy barrier Ueff of 22.9 cm−1, while the thermodynamical properties of Gd12 confirm a large magnetocaloric effect: S(7 T) − S(0 T) = 20R = 166 J mol−1 K), typical for isotropic GdIII derivatives, with ΔS = S(7 T) − S(0 T) = 1.7R for each GdIII ion.

Graphical abstract: Aggregation of [LnIII12] clusters by the dianion of 3-formylsalicylic acid. Synthesis, crystal structures, magnetic and luminescence properties

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Supplementary files

Article information


Submitted
20 Nov 2018
Accepted
24 Dec 2018
First published
26 Dec 2018

Dalton Trans., 2019,48, 1700-1708
Article type
Paper

Aggregation of [LnIII12] clusters by the dianion of 3-formylsalicylic acid. Synthesis, crystal structures, magnetic and luminescence properties

A. S. Dinca, A. Mindru, D. Dragancea, C. Tiseanu, S. Shova, S. Cornia, L. M. Carrella, E. Rentschler, M. Affronte and M. Andruh, Dalton Trans., 2019, 48, 1700
DOI: 10.1039/C8DT04602F

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