Ana B. Arauzo

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.

Homoleptic organoderivatives of high-valent nickel(III).

Homoleptic perhalophenyl derivatives of divalent nickel complexes with the general formula [NBu(4)](2)[Ni(II)(C(6)X(5))(4)] [X=F (1), Cl (2)] have been prepared by low-temperature treatment of the halo-complex precursor [NBu(4)](2)[NiBr(4)] with the corresponding organolithium reagent LiC(6)X(5). Compounds 1 and 2 are electrochemically related by reversible one-electron exchange processes with the corresponding organometallate(III) compounds [NBu(4)][Ni(III)(C(6)X(5))(4)] [X=F (3), Cl (4)]. The potentials of the [Ni(III)(C(6)X(5))(4)](-)/[Ni(II)(C(6)X(5))(4)](2-) couples are +0.07 and -0.11 V for X=F or Cl, respectively. Compounds 3 and 4 have also been prepared and isolated in good yield by chemical oxidation of 1 or 2 with bromine or the amminium salt [N(C(6)H(4)Br-4)(3)][SbCl(6)]. The [Ni(III)(C(6)X(5))(4)](-) species have SP-4 structures in the salts 3 and 4, as established by single-crystal X-ray diffraction methods. The [Ni(II)(C(6)F(5))(4)](2-) ion in the parent compound 1 has also been found to exhibit a rather similar SP-4 structure. According to their SP-4 geometry, the Ni(III) compounds (d(7)) behave as S=1/2 systems both at microscopic (EPR) and macroscopic levels (ac and dc magnetization measurements). The spin Hamiltonian parameters obtained from the analysis of the magnetic behavior of 3 and 4 within the framework of ligand field theory show that the unpaired electron is centered mainly on the metal atom, with >97 % estimated d(z(2) ) contribution. Thermal decomposition of 3 and 4 proceeds with formation of the corresponding C(6)X(5)--C(6)X(5) coupling compounds.

Antiferromagnetic single-chain magnet slow relaxation in the {Tb(α-fur)3}n polymer with non-Kramers ions

We report the synthesis, crystal structure and magnetic properties of a new molecular complex based on a Tb(III) ion supported by 2-furancarboxylic molecules: {Tb(α-fur)3(H2O)3}n (α-fur = C4H3OCOO). Two slightly different Tb sites (A and B) exist depending on the position of one of the dangling ligands. Ab initio calculations predict that, for both sites, the magnetic ground state is highly anisotropic (gz* = 17.8) and consists of a quasi-doublet with a small gap, well isolated from the next excited state. The α-fur ligand forms 1D polymeric chains of Tb ions of the same type (either A or B) running along the c-axis. The crystal structure is formed by the supramolecular stacking along the a-axis of 2D layers containing parallel chains of the same type. Static magnetization and heat capacity measurements show that, magnetically, the system can be modeled as an ensemble of Ising chains of non-Kramers Tb ions with effective spin S* = 1/2, antiferromagnetically (AF) coupled by a weak intrachain interaction (J*/kB = −0.135 K). At very low temperatures, the static susceptibility reflects the presence of a 2–4% concentration of defects in the chains. Ac susceptibility measurements at H = 0 performed down to mK temperatures have enabled us to observe the slow relaxation of magnetization through two different pathways. They are assigned to Single-Chain-Magnet (SCM) behavior in two different types of AF chains (A and B), triggered by the existence of defects breaking the chains into segments with short-range order. At temperatures below 0.1 K this mechanism is replaced by individual relaxation of the ions through direct processes. Under the application of a magnetic field the system slowly relaxes by two distinct direct processes, strongly affected by a phonon bottleneck effect.

Homoleptic Organocobalt(III) Compounds with Intermediate Spin

Homoleptic organocobalt(III) compounds with formula [NBu4][Co(III)(C6X5)4] [X = F (3), Cl (4)] were obtained in reasonable yields by chemical oxidation of the corresponding divalent species [NBu4]2[Co(II)(C6X5)4] [X = F (1), Cl (2)]. The [Co(III)(C6X5)4](-)/[Co(II)(C6X5)4](2-) couples are electrochemically related by quasi-reversible, one-electron exchange processes at moderate potential: E1/2 = -0.29 (X = F) and -0.36 V (X = Cl) versus saturated calomel electrode. The [Co(III)(C6X5)4](-) anions in salts 3 and 4 show an unusual square-planar geometry as established by single-crystal X-ray diffraction methods. According to their stereochemistry, these Co(III) derivatives (d(6)) are paramagnetic non-Kramers systems with a large zero-field splitting contribution and no observable electron paramagnetic resonance (EPR) spectrum. The thermal dependence of their magnetic susceptibilities can be explained in terms of a spin-Hamiltonian formalism with S = 1 ground state (intermediate spin) and substantial spin-orbit contribution. The magnetic properties of the square-planar d(7) parent species [NBu4]2[Co(II)(C6X5)4] were also thoroughly studied both at microscopic (EPR) and macroscopic levels (alternating current and direct current magnetization measurements). They behave as S = 1/2 (low spin) systems with mainly (dz(2))(1) electron configuration and a certain degree of s-orbital admixture that has been quantified. The electronic structures of all four open-shell [Co(C6X5)4](q-) compounds (q = 1, 2) accounting for their respective magnetic properties are based on a common orbital energy-level diagram.

Studies on a “Disappearing Polymorph”: Thermal and Magnetic Characterization of α-p-NCC6F4CNSSN•

The α-and β-phases of the thiazyl radical p-NCC6F4CNSSN• (1) can be selectively prepared by careful control of the sublimation conditions, with the α-phase crystallizing preferentially when the substrate temperature is maintained below -10 °C, whereas the β-phase is isolated when the substrate temperature is maintained at or above ambient temperature. Differential scanning calorimatry studies reveal that the α-phase converts to the β-phase upon warming over the range 111-117 °C (ΔH = +4 kJ·mol-1) via a melt-recrystallization process, with the β-phase itself melting at 167-170 °C (ΔHfus = 27 kJ·mol-1). IR and Raman spectroscopy can be used to clearly discriminate between 1α and 1β. The α-phase shows a broad maximum in the magnetic susceptibility around 8 K that, coupled with a broad maximum in the heat capacity, is indicative of short-range order. Some field dependence of the susceptibility below 3 K is observed, but the lack of features in the ac susceptibility, M vs H plots, or heat capacity mitigates against long-range order in 1α.

σ-Organoniobium Compounds with [NbR4]− and NbR4 Stoichiometries†

This work was supported by the Spanish MICINN (DGPTC)/FEDER (projects CTQ2008-06669-C02-01/BQU and MAT2008-03461/MAT) and the Gobierno de Aragon (Grupo de Excelencia: Quimica Inorganica y de los Compuestos Organometalicos).

Heteronuclear {TbxEu1−x} furoate 1D polymers presenting luminescent properties and SMM behavior

We report the synthesis, crystal structure and photo-magnetic properties of novel Tb/Eu polymeric complexes of general formula {TbxEu1−x(α-fur)3(H2O)3}n, supported by 2-furancarboxilic acid: the homonuclear Tb(III) complex {Tb} (1), four heterodinuclear complexes, {Tb0.8Eu0.2} (2), {Tb0.7Eu0.3} (3), {Tb0.3Eu0.7} (4), and {Tb0.1Eu0.9} (5), and the homonuclear Eu(III)-only complex {Eu} (6). X-ray diffraction experiments show that the α-furoate ligands, acting in bridging mode, consolidate the 1D polymeric chains along the c-axis. Luminescence studies show the sensitization capability of the furoic acid ligand. Color tuning from green to red can be successfully achieved through the heterodinuclear strategy. We have measured Eu emission by direct excitation at the resonant 7F0 → 5L6 (395 nm), and indirectly, by excitation of the non-resonant wavelength (280 nm) which provokes ligand → Tb → Eu energy transfer. Besides, ac susceptibility measurements under varying frequencies and temperatures reveal that mixed {TbxEu1−x} complexes exhibit field-induced slow relaxation dynamics, with extremely slow relaxation times, owing to direct processes affected by the bottleneck effect. Thus, the {TbxEu1−x} complexes represent interesting low-dimensional multifunctional materials combining both luminescent and SMM magnetic properties.

Crystal and local atomic structure of MgFeBO4, Mg0.5Co0.5FeBO4 and CoFeBO4: Effects of Co substitution

Single crystalline MgFeBO_4, Mg_0.5Co_0.5FeBO_4 and CoFeBO_4 have been grown by the flux method. The samples have been characterized by X-ray spectral analysis, X-ray diffraction and X-ray absorption spectroscopy. The X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra have been measured at the Fe andCoK-edges over a wide temperature range (6.5 - 300 K). The composition, the charge state and local environment of both Fe and Co atoms have been determined. The effects of Mg substitution by Co on the local structural distortions have been revealed experimentally and the M-O bond anisotropy has been found.

AC response of 2H–NbSe2 single crystals with electron-irradiation-induced defects

The generation of defects in NbSe(2) single crystals by electron irradiation has been investigated by a combination of ac susceptibility and structural measurements. Remarkably, thanks to the layered structure of NbSe(2), we show that electronic irradiation cannot only create point defects but also in-plane extended defects, which modify anisotropically the ac response. Indeed, the analysis of the onset of the nonlinear susceptibility response, H(ac)(l)(T), as a function of irradiation dose and field orientation shows a correlated increase in the density of anisotropic defects induced by electron irradiation. Also, we measured a decrease in the strength of the pinning (Labusch) constant α(L) accounting for elastic vortex oscillations within the linear Campbell regime for high-dose-irradiated samples in a transverse field, again compatible with the presence of planar defects hindering vortex pinning. X-ray powder diffraction and TEM electron diffraction measurements suggest these in-plane defects may result from the rupture of Se-Se bonds and the formation of nanorods and nanowires by NbSe(2) sheet rolling.

Note: A sample holder design for sensitive magnetic measurements at high temperatures in a magnetic properties measurement system

A sample holder design for high temperature measurements in a commercial MPMS SQUID magnetometer from Quantum Design is presented. It fulfills the requirements for the simultaneous use of the oven and reciprocating sample option (RSO) options, thus allowing sensitive magnetic measurements up to 800 K. Alternating current susceptibility can also be measured, since the holder does not induce any phase shift relative to the ac driven field. It is easily fabricated by twisting Constantan© wires into a braid nesting the sample inside. This design ensures that the sample be placed tightly into a tough holder with its orientation fixed, and prevents any sample displacement during the fast movements of the RSO transport, up to high temperatures.