Giulia Lorusso

A dense metal-organic framework for enhanced magnetic refrigeration

X iv :1 21 2. 28 77 v1 [ co nd -m at .m tr lsc i] 1 2 D ec 2 01 2 Magnetic cryocooling with Gd centers in a light and compact framework G. Lorusso, J. W. Sharples, E. Palacios, O. Roubeau, E. K. Brechin, R. Sessoli, A. Rossin, F. Tuna, E. J. L. McInnes, D. Collison, and M. Evangelisti a) Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC − Universidad de Zaragoza, Departamento de F́ısica de la Materia Condensada, 50009 Zaragoza, Spain School of Chemistry and Photon Science Institute, The University of Manchester, M13-9PL Manchester, United Kingdom School of Chemistry, The University of Edinburgh, EH9-3JJ Edinburgh, United Kingdom Department of Chemistry and INSTM, Università degli Studi di Firenze, 50019 Sesto Fiorentino, Italy Istituto di Chimica dei Composti Organometallici (ICCOM), CNR, 50019 Sesto Fiorentino, ItalyThe three-dimensional metal-organic framework Gd(HCOO)3 is characterized by a relatively compact crystal lattice of weakly interacting Gd(3+) spin centers interconnected via lightweight formate ligands, overall providing a remarkably large magnetic:non-magnetic elemental weight ratio. The resulting magnetocaloric effect per unit volume is decidedly superior in Gd(HCOO)3 than in the best known magnetic refrigerant materials for liquid-helium temperatures and low-moderate applied fields.

Increasing the dimensionality of cryogenic molecular coolers: Gd-based polymers and metal–organic frameworks

The magnetothermal properties of a coordination polymer and a metal-organic framework (MOF) based on Gd(3+) ions are reported. An equally large cryogenic magnetocaloric effect (MCE) is found, irrespective of the dimensionality. This combined with their robustness makes them appealing for widespread magnetic refrigeration applications.

Fluoride-Bridged {GdIII3MIII2} (M=Cr, Fe, Ga) Molecular Magnetic Refrigerants†

The reaction of fac-[M(III)F3(Me3tacn)]⋅x H2O with Gd(NO3)3⋅5H2O affords a series of fluoride-bridged, trigonal bipyramidal {Gd(III)3M(III)2} (M = Cr (1), Fe (2), Ga (3)) complexes without signs of concomitant GdF3 formation, thereby demonstrating the applicability even of labile fluoride-complexes as precursors for 3d-4f systems. Molecular geometry enforces weak exchange interactions, which is rationalized computationally. This, in conjunction with a lightweight ligand sphere, gives rise to large magnetic entropy changes of 38.3 J kg(-1)  K(-1) (1) and 33.1 J kg(-1)  K(-1) (2) for the field change 7 T→0 T. Interestingly, the entropy change, and the magnetocaloric effect, are smaller in 2 than in 1 despite the larger spin ground state of the former secured by intramolecular Fe-Gd ferromagnetic interactions. This observation underlines the necessity of controlling not only the ground state but also close-lying excited states for successful design of molecular refrigerants.

A ferromagnetically coupled diphenoxo-bridged Gd3+-Mn2+ dinuclear complex with a large magneto-caloric effect

A novel diphenoxo-bridged Gd(3+)-Mn(2+) dimer is proposed as a good candidate for cryogenic magnetic refrigeration. The large MCE is enhanced by the ferromagnetic interaction between the two metal ions.

Molecular Nanoscale Magnetic Refrigerants: A Ferrimagnetic {CuII15GdIII7} Cagelike Cluster from the Use of Pyridine-2,6-dimethanol

The employment of pyridine-2,6-dimethanol in 3d/4f metal cluster chemistry has afforded a new {Cu(II)15Gd(III)7} cagelike molecule with a beautiful structure built by fused triangular subunits; the compound exhibits an overall ferrimagnetic behavior with an appreciable ground-state spin value and shows promise as a low-temperature magnetic refrigerant.

Decanuclear Ln10 Wheels and Vertex‐Shared Spirocyclic Ln5 Cores: Synthesis, Structure, SMM Behavior, and MCE Properties

The reaction of a Schiff base ligand (LH3) with lanthanide salts, pivalic acid and triethylamine in 1:1:1:3 and 4:5:8:20 stoichiometric ratios results in the formation of decanuclear Ln10 (Ln = Dy (1), Tb (2), and Gd (3)) and pentanuclear Ln5 complexes (Ln = Gd (4), Tb (5), and Dy (6)), respectively. The formation of Ln10 and Ln5 complexes are fully governed by the stoichiometry of the reagents used. Detailed magnetic studies on these complexes (1-6) have been carried out. Complex 1 shows a SMM behavior with an effective energy barrier for the reversal of the magnetization (Ueff) = 16.12(8) K and relaxation time (τo) = 3.3×10(-5) s under 4000 Oe direct current (dc) field. Complex 6 shows the frequency dependent maxima in the out-of-phase signal under zero dc field, without achieving maxima above 2 K. Complexes 3 and 4 show a large magnetocaloric effect with the following characteristic values: -ΔSm = 26.6 J kg(-1) K(-1) at T = 2.2 K for 3 and -ΔSm = 27.1 J kg(-1) K(-1) at T = 2.4 K for 4, both for an applied field change of 7 T.

Magnetic “Molecular Oligomers” Based on Decametallic Supertetrahedra: A Giant Mn49 Cuboctahedron and its Mn25Na4 Fragment

Two nanosized Mn49 and Mn25Na4 clusters based on analogues of the high-spin (S=22) [Mn(III)6Mn(II)4(μ4-O)4](18+) supertetrahedral core are reported. Mn49 and Mn25Na4 complexes consist of eight and four decametallic supertetrahedral subunits, respectively, display high virtual symmetry (O(h)), and are unique examples of clusters based on a large number of tightly linked high nuclearity magnetic units. The complexes also have large spin ground-state values (Mn49: S=61/2; Mn25Na4: S=51/2) with the Mn49  cluster displaying single-molecule magnet (SMM) behavior and being the second largest reported homometallic SMM.

Surface-confined molecular coolers for cryogenics

An excellent molecule-based cryogenic magnetic refrigerant, gadolinium acetate tetrahydrate, is here used to decorate selected portions of silicon substrate. By quantitative magnetic force microscopy for a variable applied magnetic field near liquid-helium temperature, the molecules are demonstrated to hold their magnetic properties intact, and therefore their cooling functionality, after their deposition. These results represent a step forward towards the realization of a molecule-based micro-refrigerating device at very low temperatures.

Chemical control of spin propagation between heterometallic rings

We present a synthetic, structural, theoretical, and spectroscopic study of a family of heterometallic ring dimers which have the formula [{Cr(7)NiF(3)(Etglu)(O(2)CtBu)(15)}(2)(NLN)], in which Etglu is the pentadeprotonated form of the sugar N-ethyl-D-glucamine, and NLN is an aromatic bridging diimine ligand. By varying NLN we are able to adjust the strength of the interaction between rings with the aim of understanding how to tune our system to achieve weak magnetic communication between the spins, a prerequisite for quantum entanglement. Micro-SQUID and EPR data reveal that the magnetic coupling between rings is partly related to the through-bond distance between the spin centers, but also depends on spin-polarization mechanisms and torsion angles between aromatic rings. Density functional theory (DFT) calculations allow us to make predictions of how such chemically variable parameters could be used to tune very precisely the interaction in such systems. For possible applications in quantum information processing and molecular spintronics, such precise control is essential.

CO2 as a reaction ingredient for the construction of metal cages: a carbonate-panelled [Gd6Cu3] tridiminished icosahedron

A CO3(2-)-panelled [Gd(III)6Cu(II)3] cage conforming to a tridiminished icosahedron is synthesised by bubbling CO2 through a solution of Gd(III) and Cu(II) ions.