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Building 1D lanthanide chains and non-symmetrical [Ln2] “triple-decker” clusters using salen-type ligands: magnetic cooling and relaxation phenomena

AutorLorusso, Giulia; Evangelisti, Marco; Milios, Constantinos J.
Fecha de publicación2016
EditorRoyal Society of Chemistry (Great Britain)
CitaciónDalton Transactions 45(46): 18591-18602 (2016)
ResumenA solvothermal reaction between Ln(NO)·6HO (Ln: Gd, Tb and Dy), 2-hydroxy-1-naphthaldehyde, 2-OH-naphth, and ethylenediamine, en, in MeOH in the presence of a base, NEt, led to the formation of the 1D coordination polymers [Ln(L)(MeO)(MeOH)]·MeOH (Ln = Gd (1·MeOH), Tb(2), Dy (3·MeOH); HL = 1,1′-((1E,1′E)-(ethane-1,2-diylbis(azanylylidene))bis(methanylylidene))bis(naphthalen-2-ol), the Schiff-base ligand derived from the condensation of 2-OH-naphth and en), while a similar reaction in an excess of NaN yielded 1D coordination polymers [Ln(L)(N)(MeO)(MeOH)] (Ln = Gd (4), Tb (5), Dy (6)). Finally, upon replacing ethylenediamine with o-phenylenediamine, o-phen, we managed to isolate the discrete dimers [Dy(L′)(MeOH)]·2MeOH (7·2MeOH) and [Gd(L′)(MeOH)]·2MeOH (8·2MeOH) (HL′ = 1,1′-((1E,1′E)-(1,2-phenylenebis(azanylylidene))bis(methanylylidene))bis (naphthalen-2-ol), the Schiff-base ligand from the condensation of 2-OH-naphth and o-phen). Polymers 1-3 describe one-dimensional chains, containing alternating seven- and eight-coordinate Ln metal centers, polymers 4-6 contain eight-coordinate lanthanide ions, while in both 7 and 8 the two Ln centers are eight- and seven-coordinate, adopting square antiprismatic and “piano-stool” geometry, respectively. The magnetocaloric properties of the three Gd analogues were determined from magnetic measurements, yielding the magnetic entropy change-ΔS = 21.8, 23.0 and 16.0 J kg K at T = 3.0 K on demagnetization of 7 T to 0, for 1, 4 and 8, respectively. The study of the magnetic properties also revealed that all three Dy analogues (3, 6 and 7) display out-of-phase signals, therefore suggesting slow magnetic relaxation, while such behaviour was not established in the Tb analogues.
Descripciónet al.
Versión del editorhttps://doi.org/10.1039/c6dt02932a
URIhttp://hdl.handle.net/10261/148638
DOI10.1039/c6dt02932a
Identificadoresdoi: 10.1039/c6dt02932a
e-issn: 1477-9234
issn: 1477-9226
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