Aggregation of [Ln III 12] clusters by the dianion of 3-formylsalicylic acid. Synthesis, crystal structures, magnetic and luminescence properties
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Dalton Transactions
Numărul 5(48) / 2019 / ISSN 1477-9226

Aggregation of [Ln III 12] clusters by the dianion of 3-formylsalicylic acid. Synthesis, crystal structures, magnetic and luminescence properties


DOI: 10.1039/c8dt04602f
Pag. 1700-1708

Autor Nou1, Dragancea Diana2, Shova Sergiu3, Rentschler Eva4, Affronte M.5, Andruh Marius1
 
1 Universitatea din Bucureşti,
2 Institutul de Chimie,
3 Institutul de Chimie Macromoleculara „Petru Poni“, Iaşi,
4 Universitatea Johannes Gutenberg din Mainz,
5 Università di Modena e Reggio Emilia, Modena
 
Disponibil în IBN: 1 martie 2019


Rezumat

Three isostrucutral dodecanuclear clusters with the general formula [Ln12(fsa)12(μf3-OH)12(DMF)12]·nDMF (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.