Issue 37, 2024

Magnetocaloric effect in 1D-polymers bearing 15-metallacrown-5 {GdCu5}3+ units and anionic oxalate complexes

Abstract

Two complexes {[GdCu5(GlyHA)5(H2O)7Cr(C2O4)3]·11.02H2O}n (1) and {{[GdCu5(GlyHA)5(H2O)62-[Cu(C2O4)2(H2O)]}2μ4-[Cu(C2O4)2]·15.8H2O}n (2), were obtained as outcomes of the reactions between the cationic hexanuclear {GdCu5(GlyHA)5}3+ 15-metallacrown-5 complex (where GlyHA2− = glycinehydroxamate) and the anionic oxalate complexes K3[Cr(C2O4)3] or K2[Cu(C2O4)2]. Both 1 and 2 possess polymeric 1D-chain structures according to X-ray structural analysis. As a consequence of the geometric orientations of the donor atoms in the oxalates from [Cr(C2O4)3]3−, the Cu5 mean planes of neighboring 15-metallacrown-5 units {GdCu5(GlyHA)5}3+ are angled at 75.5° to each other, which leads to formation of a zig-zag motif in the 1D-chains of complex 1. The centrosymmetric complex 2 contains two structurally different bis(oxalato)cuprate anions μ2-[Cu(C2O4)2(H2O)]2−, for one of which, coordination to two adjacent {GdCu5(GlyHA)5}3+ units leads to formation of linear 1D-chains in 2, while the second type, μ4-[Cu(C2O4)2]2−, is coordinated to four {GdCu5(GlyHA)5}3+ units, causing the cross-linking of single 1D-chains into a double-chain 1D coordination polymer. Studies of χMT vs. T data for 1 and 2 in a 2–300 K temperature range revealed the presence of both ferromagnetic and antiferromagnetic interactions amongst paramagnetic centres. The experimental χMT vs. T data for 1 were fitted using a model which takes into account exchange interactions between adjacent copper(II) ions, the Gd–Cu exchange interactions within {GdCu5(GlyHA)5}3+ units and additionally Gd–Cr exchange interactions. Fitting of the χMT vs. T data for 2 was not possible, since coordination of μ4-[Cu(C2O4)2]2− to {GdCu5(GlyHA)5}3+ led to the non-equivalence of several Cu–Cu exchange interactions within the metallacrown units and hence a superfluity of fittable parameters. Complexes 1 and 2 are the first examples of 15-metallacrown-5 complexes demonstrating a magnetocaloric effect (−ΔSM at 13 T reaches 24.26 J K−1 kg−1 at 5 K and 19.14 J K−1 kg−1 at 4 K for 1 and 2, respectively).

Graphical abstract: Magnetocaloric effect in 1D-polymers bearing 15-metallacrown-5 {GdCu5}3+ units and anionic oxalate complexes

Supplementary files

Article information

Article type
Paper
Submitted
25 Aug 2024
Accepted
02 Sep 2024
First published
04 Sep 2024
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2024,53, 15713-15724

Magnetocaloric effect in 1D-polymers bearing 15-metallacrown-5 {GdCu5}3+ units and anionic oxalate complexes

A. V. Pavlishchuk, S. V. Kolotilov, M. Zeller, V. V. Pavlishchuk, F. Pointillart and A. W. Addison, Dalton Trans., 2024, 53, 15713 DOI: 10.1039/D4DT02413C

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