Dodecanuclear [NiII8Ln4] clusters and rings of corner-sharing {NiII2Ln2} cubanes (Ln = Dy, Gd, Y}; Magnetic and Magnetothermal properties

Thomais G. Tziotzi, Eleftheria Agapaki, Emmanouil Κ. Charkiolakis, David Gracia, Marc Ubach I Cervera, Scott Dalgarno, Marco Evangelisti, Euan K. Brechin, Constantinos J. Milios

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Abstract

The solvothermal reaction of NiCl2·6H2O with 1,3,5-tri(2-hydroxyethyl)-1,3,5-triazacyclohexane, LH3, and Ln(OAc)3·4H2O in the presence of salicylaldehyde in MeOH leads to the formation of the dodecanuclear isostructural species [NiII8Ln4(L′)8(OAc)4(OH)8(H2O)4xH2O (Ln = Dy, x = 6 (1); Gd, x = 24 (2); Y, x = 10 (3); L′ = the dianion of the Schiff-base resulting from the reaction of salicylaldehyde and ethanolamine). The metallic core of the clusters describes a ring of corner-sharing {Ni2Ln2} cubanes assembled on a central, planar rectangular {Ln4} unit. Magnetization studies conducted on complexes 1–3 demonstrate the presence of dominant ferromagnetic exchange at low temperatures, which is largely attributed to the Ni⋯Ni interactions. The significant magnetocaloric effect observed in the Gd analogue has been assessed through heat capacity and magnetization measurements.

Original languageEnglish
Pages (from-to)4664-4671
Number of pages8
JournalDalton Transactions
Volume54
Issue number11
Early online date13 Feb 2025
DOIs
Publication statusPublished - 21 Mar 2025

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