Synthesis, structural, and magnetic characterization of a mixed 3d/4f 12-Metallacrown-4 family of complexes

Athanasopoulou AA, Carrella LM, Rentschler E (2018)

Publication Type: Journal article

Publication year: 2018

Journal

Inorganics MDPI

Book Volume: 6

Article Number: 66

Journal Issue: 3

DOI: 10.3390/inorganics6030066

Abstract

A new family of complexes (^tBu4N){[Ln^III(O2CBu^t)4][12-MC-Mn(III)N(shi)-4]}·5CH2Cl2 (Ln = Gd (1) and Tb (2)), (^tBu4N)2{[Y^III(O2CBu^t)4][12-MC-Mn(III)N(shi)-4]}(ClO4) (3); where shiH3 = salicylhydroxamic acid; Bu^tCO2 - = pivalate ions; ^tBu4N = tetrabutylammonium and ClO4 - = perchlorate ions, has been isolated. The reaction of salicylhydroxamic acid with Mn(O2CBu^t)2·2H2O, Ln(NO3)3·xH2O, ^tBu4NClO4 in the presence of morpholine (C4H9NO) led to the isolation of compounds 1-3. The complexes belong to the 12-MC-4 family of Metallacrowns (MCs) possessing a central {Mn4 ^IIILn^III(μ-NO)4}¹¹⁺ core with the four Mn^III atoms occupying the periphery positions, while the formed [Mn-N-O] repeating unit, assists in the accommodation of the Ln^III atom in the center of the ring. Peripheral ligation is provided by four η¹:η¹:μ pivalate ions. Direct current magnetic susceptibility (dc) measurements revealed the presence of predominant antiferromagnetic exchange interactions within the metal centers. A 1-J fitting model was used in order to quantify the Mn^III-Mn^III interactions and fitting of the data, for the diamagnetic Y^III analogue, gave J = -3.74 cm^-1 and gMn(III) = 2.07. Fitting of the {Mn4Gd} compound using a 2-J model, counting additionally for the Mn^III-Gd^III interactions, revealed values of J1 = -3.52 cm^-1, J2 = -0.45 cm^-1, and gMn(III) = 1.99.

Involved external institutions

Johannes Gutenberg-Universität Mainz (JGU)

Germany (DE)

How to cite

APA:

Athanasopoulou, A.A., Carrella, L.M., & Rentschler, E. (2018). Synthesis, structural, and magnetic characterization of a mixed 3d/4f 12-Metallacrown-4 family of complexes. Inorganics, 6(3). https://doi.org/10.3390/inorganics6030066

MLA:

Athanasopoulou, Angeliki A., Luca M. Carrella, and Eva Rentschler. "Synthesis, structural, and magnetic characterization of a mixed 3d/4f 12-Metallacrown-4 family of complexes." Inorganics 6.3 (2018).

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