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

Dinca Alina S.; Mindru Alexei; Dragancea Diana; Tiseanu Carmen D.; Shova Sergiu; Cornia Samuele; Carrella Luca M.; Rentschler Eva; Affronte M.; Andruh Marius

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1099

SM ISO690:2012

DINCA, Alina S., MINDRU, Alexei, DRAGANCEA, Diana, TISEANU, Carmen D., SHOVA, Sergiu, CORNIA, Samuele, CARRELLA, Luca M., RENTSCHLER, Eva, AFFRONTE, M., ANDRUH, Marius. Aggregation of [Ln III 12] clusters by the dianion of 3-formylsalicylic acid. Synthesis, crystal structures, magnetic and luminescence properties. In: Dalton Transactions, 2019, nr. 5(48), pp. 1700-1708. ISSN 1477-9226. DOI: https://doi.org/10.1039/c8dt04602f

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Dalton Transactions

Numărul 5(48) / 2019 / ISSN 1477-9226 /ISSNe 1477-9234

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

DOI:https://doi.org/10.1039/c8dt04602f

Pag. 1700-1708

Dinca Alina S.¹, Mindru Alexei², Dragancea Diana², Tiseanu Carmen D.³, Shova Sergiu⁴, Cornia Samuele⁵, Carrella Luca M.⁶, Rentschler Eva⁶, Affronte M.⁵, Andruh Marius¹

¹ University of Bucharest,
² Institute of Chemistry,
³ National Institute for Laser, Plasma and Radiation Physics (INFLPR),
⁴ “Petru Poni” Institute of Macromolecular Chemistry,
⁵ Università di Modena e Reggio Emilia, Modena,
⁶ Johannes Gutenberg University Mainz

Disponibil în IBN: 1 martie 2019

Rezumat

Three isostrucutral dodecanuclear clusters with the general formula [Ln₁₂(fsa)₁₂(μf₃-OH)₁₂(DMF)₁₂]·nDMF (fsa^2- 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 Ln^III ions, three μ₃-OH groups and one μ₃-oxygen atom arising from the fsa^2- 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 U_eff 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 Gd^III derivatives, with ΔS = S(7 T) - S(0 T) = 1.7R for each Gd^III ion.

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<cfAbstr cfLangCode='EN' cfTrans='o'><p>Three isostrucutral dodecanuclear clusters with the general formula [Ln<sub>12</sub>(fsa)<sub>12</sub>(&mu;f<sub>3</sub>-OH)<sub>12</sub>(DMF)<sub>12</sub>]&middot;nDMF (fsa<sup>2-</sup> is the dianion of 3-formylsalicylic acid; Ln = Eu 1, Gd 2, Dy 3) have been obtained from the reaction of fromylsalicyclic acid (H<sub>2</sub>fsa), tetrabutylammonium hydroxide and Ln(NO<sub>3</sub>)<sub>3</sub>&middot;6H<sub>2</sub>O in methanol/DMF. Their structure consists of four vertex-sharing heterocubanes. Each heterocubane unit is assembled from four Ln<sup>III</sup> ions, three &mu;<sub>3</sub>-OH groups and one &mu;<sub>3</sub>-oxygen atom arising from the fsa<sup>2-</sup> 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 U<sub>eff</sub> of 22.9 cm<sup>-1</sup>, while the thermodynamical properties of Gd<sub>12</sub> confirm a large magnetocaloric effect: S(7 T) - S(0 T) = 20R = 166 J mol<sup>-1</sup> K), typical for isotropic Gd<sup>III</sup> derivatives, with &Delta;S = S(7 T) - S(0 T) = 1.7R for each Gd<sup>III</sup> ion.</p></cfAbstr>
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