Comment on "Theoretical design of molecular nanomagnets for magnetic refrigeration" [Appl. Phys. Lett. 103, 202410 (2013)]

Garlatti et al. [Appl. Phys. Lett. 103, 202410 (2013)] report theoretical simulations aimed at showing that the best molecular nanomagnets for magnetic refrigeration between T = 10 K and sub-Kelvin region are those made of strongly ferromagnetically-coupled magnetic ions. This Comment revises such conclusion based on results that, apparently, contrast with the established belief in this research field.Comment: 3 pages, 2 figure

Magnetic "Molecular Oligomers" based on decametallic supertetrahedra: A giant Mn49 cuboctahedron and its Mn25Na4 fragment

et al.Two nanosized Mn and MnNa clusters based on analogues of the high-spin (S=22) [Mn Mn (μ-O)] supertetrahedral core are reported. Mn and MnNa complexes consist of eight and four decametallic supertetrahedral subunits, respectively, display high virtual symmetry (O), 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 (Mn: S=61/2; MnNa: S=51/2) with the Mn cluster displaying single-molecule magnet (SMM) behavior and being the second largest reported homometallic SMM.This work was supported by the Cyprus Research Promotion Foundation grant ANABAVMISH/PAGIO/0308/12 which is co-funded by the Republic of Cyprus and the European Regional Development Fund, the US National Science Foundation (Grant DMR-1213030 to G.C.), and the Spanish MINECO (Project FEDER-MAT2012-38318-C03-01).Peer Reviewe

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

et al.A 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.The research fund for CJM and ABC has been co-financed by the European Union (European Social Fund – ESF) and Greek national funds through the Operational Program “Education and Lifelong Learning” of the National Strategic Reference Framework (NSRF) – Research Funding Program: THALES. Investing in knowledge society through the European Social Fund. GL and ME thank Spanish MINECO (MAT2015-68204-R). MS, MO and TL: “Project partially supported by Wroclaw Centre of Biotechnology, programme The Leading National Research Centre (KNOW) for years 2014–2018”Peer Reviewe

Large adiabatic temperature and magnetic entropy changes in EuTiO3

Under the terms of the Creative Commons Attribution license.-- et al.We have investigated the magnetocaloric effect in single and polycrystalline samples of quantum paraelectric EuTiO3 by magnetization and heat capacity measurements. Single crystalline EuTiO3 shows antiferromagnetic ordering due to Eu2+ magnetic moments below TN=5.6K. This compound shows a giant magnetocaloric effect around its Néel temperature. The isothermal magnetic entropy change is 49Jkg-1K-1, the adiabatic temperature change is 21 K, and the refrigeration capacity is 500Jkg-1 for a field change of 7 T at TN. The single crystal and polycrystalline samples show similar values of the magnetic entropy and adiabatic temperature changes. The large magnetocaloric effect is due to suppression of the spin entropy associated with the localized 4f moment of Eu2+ ions. The giant magnetocaloric effect, together with negligible hysteresis, suggest that EuTiO3 could be a potential material for magnetic refrigeration below 40 K.R.M. acknowledges the support of MOE Tier 1 Grant No. R144-000-308-112. J.-S.W. acknowledges the support of MOE Tier 2 Grant No. R144-000-349-112. M.E. acknowledges financial support from MINECO through Grant No. FEDER-MAT2012-38318-C03-01.Peer Reviewe

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 variable applied magnetic field near liquid-helium temperature, we demonstrate that the molecules hold intact their magnetic properties, and therefore their cooling functionality, after their deposition. Our result represents a step forward towards the realization of a molecule-based microrefrigerating device for very low temperatures.Comment: 16 pages, 4+1 figures, S.I. available from author

Decanuclear Ln10 wheels and vertex-shared spirocyclic Ln5 cores: synthesis, structure, SMM behavior, and MCE properties

et al.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.We are thankful to the Department of Science and Technology, New Delhi, for financial support. S.D., A.D., S.K., and S.B. thank CSIR, India for Senior Research Fellowship. V.C. is thankful to the Department of Science and Technology for a J.C. Bose National Fellowship. EC is thankful for financial support to Ministerio de Economía y Competitividad (MINECO) for Projects CTQ-2011-24478, CTQ2014-56312-P, the Junta de Andalucía (FQM-195 and the Project of excellence P11-FQM-7756), the University of Granada financial support. M.E. acknowledges financial support from MINECO through grant MAT2012-38318-C03-01. ST thanks the Junta de Andalucía for a postdoctoral contract.Peer Reviewe

Layered gadolinium hydroxides for low-temperature magnetic cooling

Layered gadolinium hydroxides have revealed to be excellent candidates for cryogenic magnetic refrigeration. These materials behave as pure 2D magnetic systems with a Heisenberg-Ising critical crossover, induced by dipolar interactions. This 2D character and the possibility offered by these materials to be delaminated open the possibility of rapid heat dissipation upon substrate deposition.We are grateful to the EU (ERC Advanced Grant SPINMOL), the Spanish MINECO (Projects MAT-2014-56143-R, CTQ-2014-59209-P and FEDER-MAT2012-38318-C03-01), and the Generalitat Valenciana (Prometeo Program and ISIC-Nano). Support from INNCIDE program through Vicerectorat d’lnvestigacio i Política Científica of the University of Valencia is also acknowledged. G. A. thanks the EU for a Marie Curie Fellowship (FP7/2013-IEF-627386). G.M.E. thanks the Spanish MINECO for a Ramón y Cajal Fellowship.Peer Reviewe

Effects of polluted air-masses advection on atmospheric particles in a semi-rural site in south Italy by SEM-EDX analysis

The variation of aerosol properties under polluted air masses advection was studied in a semi-rural site in South Italy, by means of SEM-EDX analysis performed on particles collected on 13-stages impactor filters. Radiometric measurements, HYSPLIT back-trajectories and NAAPS maps helped to choose four measurement days of polluted air mass circulation, two of them collected in the warm season (31 July 2008, 16 September 2010) and two in the cold one (16 April 2009, 18 March 2010). Polluted aerosol characteristics were compared to those under background (BG) conditions (8 February 2011), highlighting differences in the particles chemical and morphological properties. One of the signatures of the air mass transport in the coarse fraction was the higher content of particles containing S, i.e., S-reacted, (27.5% on average) in comparison with BG conditions (1%). Two main sources of transported aerosols were identified: industrial processes and biomass burning, with fly ash, metal and S-rich particles in the first case, and K-salts and nitrate-coated Ca-bearingparticles in the second. Single particle analysis on the coarse fraction allowed large agglomerates of soot to be identified, with inclusions of silicate particles rich in Cu and Zn, Ca-S, fly ash and metals particles that are a clear indication of extensive modifications of aerosol size, chemical composition and, likely, radiative properties. In finer stages (EAD ≤ 0.94 μm) concurrent collection of organic and inorganic particles originated an agglomerate state matter mainly characterized by K and S for polluted conditions and by K only for BG

Refrigeradores moleculares

En este trabajo se pretende hacer una aportación en el campo de la criogenia, en particular, aplicar las nuevas tecnologías micrométricas y el uso de moléculas magnéticas, que pueden presentar efectos magnetocalóricos muy grandes en el rango de bajas temperaturas, para el desarrollo de refrigeradores en chip. Dentro de lo ambicioso de este proyecto, los dos objetivos han sido contribuir al desarrollo de los microchips, en concreto, fabricar un termómetro de alta resolución para bajas temperaturas, y el estudio del orden magnético y las propiedades magnetocalóricas de un material magnético de base molecular, el Formiato de Gadolinio, que podría utilizarse como refrigerante.<br /

Dodecanuclear 3d/4f-metal clusters with a 'Star of David' topology: Single-molecule magnetism and magnetocaloric properties

A family of interwoven molecular inorganic knots, shaped like the 'Star of David', was prepared by the employment of naphthalene-2,3-diol in 3d/4f-metal cluster chemistry; the isoskeletal dodecanuclear compounds exhibit slow relaxation of the magnetization and magnetocaloric properties, depending on the metal ion.This work was supported by Brock University, NSERC-DG and ERA (to Th.C.S), the Ontario Trillium Foundation (graduate scholarship to D.I.A), the Fundaçao para a Ciencia e a Tecnologia (FCT, Portugal) financial support to REQUIMTE/LAQV (UID/ QUI/50006/2013), the European Synchrotron Radiation Facility (Grenoble, France) (for granting access time to the Swiss Norwegian BM01a beamline under the CH-3613 and CH-3849 research proposals), MINECO (FEDER-MAT2012-38318-C03 to M. E and postdoctoral contract to G. L), and the National Natural Science Foundation of China (grants 21371166, 21331003 and 21221061 to J. T).Peer Reviewe