Superconducting spin valve effect in Co/Pb/Co heterostructures with insulating interlayers.

We report the superconducting properties of Co/Pb/Co heterostructures with thin insulating interlayers. The main specific feature of these structures is the intentional oxidation of both superconductor/ferromagnet (S/F) interfaces. We study the variation of the critical temperature of our systems due to switching between parallel and antiparallel configurations of the magnetizations of the two magnetic layers. Common knowledge suggests that this spin valve effect, which is due to the S/F proximity effect, is most pronounced in the case of perfect metallic contacts at the interfaces. Nevertheless, in our structures with intentionally deteriorated interfaces, we observed a significant full spin valve effect. A shift of the superconducting transition temperature Tc by switching the mutual orientation of the magnetizations of the two ferromagnetic Co layers from antiparallel to parallel amounted to ΔTc = 0.2 K at the optimal thickness of the superconducting Pb layer. Our findings verify the so far unconfirmed earlier results by Deutscher and Meunier on an F1/S/F2 heterostructure with oxidized interlayers [Deutscher, G.; Meunier, F. Phys. Rev. Lett. 1969, 22, 395. https://doi.org/10.1103/PhysRevLett.22.395] and suggest an alternative route to optimize the performance of superconducting spin valves.

Effect of Foliar Sodium Selenate and Nano Selenium Supply on Biochemical Characteristics, Essential Oil Accumulation and Mineral Composition of Artemisia annua L.

Selenium (Se) biofortification of aromatic plants is a promising strategy to produce valuable functional food with high biological activity and enhanced essential oil yield. The experiment carried out in 2021 and 2022 on A. annua treated with sodium selenate or nano-Se sprayed on foliar apparatus demonstrated a significant increase in photosynthetic pigments, pectin, waxes, macro- and microelements and a decrease in malonic dialdehyde (MDA) accumulation. Contrary to literature reports, neither selenate nor nano-Se showed a beneficial effect on essential oil accumulation; the oil yield did not differ between the selenate treated and control plants but was halved by the nano-Se application. Extremely high variations in the number of essential oil components, as well as in the eucalyptol, artemisia ketone, camphor and germacrene D ratio in the 2021 and 2022 experiments were recorded. The analysis of the 2016-2022 data for oil yield and composition in the control plants revealed a direct correlation between the number of components and of solar flares, and a negative correlation between oil yield and the percentage of spotless days. Both control plants and plants fortified with selenium showed higher levels of germacrene D and lower levels of artemisia ketone in 2022, characterized by more remarkable solar activity compared to 2021. Nano-Se supply resulted in the highest percentage of germacrene D accumulation. The results of the present research highlight the importance of the solar activity effect on the essential oil yield and quality of aromatic plants.

Low-Dimensional Magnetism in Multivariate Copper/Zinc MOF-74 Materials Formed via Different Mechanochemical Methods.

MOF-74 is an archetypal magnetic metal-organic framework (MOF) family, with metal nodes bridged by 2,5-dioxido-1,4-benzenedicarboxylic acid (H4dobdc) and arranged into one of the simplest representations of the 1D Ising magnetic model. Recently, a novel mechano-synthetic approach opened a pathway toward a series of bimetallic multivariate (1:1) M1M2-MOF-74 materials, with the uniform distribution of metal cations in the oxometallic chains, offering a unique opportunity to investigate low-dimensional magnetism in these heterometallic MOFs. We explore here how different mechanochemical procedures affect the interaction between the metal nodes of the model system of three multivariate copper(II)/zinc(II)-MOF-74 materials, two of which were obtained through a template-controlled procedure, and the third one was obtained by recently developed mechanical MOF-alloying combined with subsequent accelerated aging. While the three Cu/Zn-MOF-74 products have almost identical powder X-ray diffraction (PXRD) diffractograms and Fourier transform infrared spectra, they differ significantly in their magnetic properties, as revealed through detailed magnetization and X-band and multifrequency high-field electron spin resonance measurements. The magnetic results of the three multivariate Cu/Zn-MOF-74s were compared to the properties of the monometallic Cu-MOF-74, which shows antiferromagnetic intrachain and weaker ferromagnetic interchain interactions. Energy-dispersive X-ray spectroscopy/scanning electron microscopy and solid-state nuclear magnetic resonance spectroscopy helped rationalize the observed differences in magnetization, and in situ synchrotron PXRD monitoring of template-controlled MOF formation revealed different reaction pathways when using the zinc or copper intermediates, involving even the fleeting occurrence of a rare MOF-74 polymorph.

A mononuclear iron(III) complex with unusual changes of color and magneto-structural properties with temperature: synthesis, structure, magnetization, multi-frequency ESR and DFT study.

From the reaction of 2-hydroxy-6-methylpyridine (L) with iron(II) tetrafluoroborate, a new mononuclear iron(III) octahedral complex [FeL6](BF4)3 has been isolated. The color of the complex reversibly changed from red at room temperature to yellow-orange at the liquid nitrogen temperature. Magnetization measurements indicate that iron(III) in [FeL6](BF4)3 is in a high-spin state S = 5/2, from room temperature to 1.8 K. The high-spin ground state of iron(III) is also confirmed by DFT calculations. Although the spin-crossover of the complex is not observed, X-band and multifrequency high-field/high-frequency electron spin resonance (ESR) spectroscopy shows rather uncommon iron(III) spectra at room temperature and an unusual change with cooling. Spectral simulations reveal that the S = 5/2 ground state multiplet of the complex can be characterized by the temperature independent axial zero-field splitting parameter of |D| = +2 GHz (0.067 cm-1) while the value of the rhombic parameter E of the order of some tenths MHz increases on lowering the temperature. Single crystal X-ray diffraction (SCXRD) shows that the iron(III) coordination geometry does not change with temperature while supramolecular interactions are temperature dependent, influencing the iron(III) rhombicity. Additionally, the DFT calculations show temperature variation of the HOMO-LUMO gap, in agreement with the changes of color and ESR-spectra of the iron(III) complex with temperature.

Temperature-dependent dynamics of endohedral fullerene Sc2@C80(CH2Ph) studied by EPR spectroscopy.

Endohedral fullerenes are promising materials for the quantum information and quantum processing due to the unique properties of the electron-nuclear spin system well isolated from the environment inside the fullerene cage. The endofullerene Sc2@C80(CH2Ph) features a strong hyperfine interaction between one electron spin 1/2 localized at the Sc2 dimer and two equivalent 45Sc nuclear spins 7/2, which yields 64 well resolved EPR transitions. We report a comprehensive analysis of the temperature dependence of the EPR spectrum of Sc2@C80(CH2Ph) dissolved in d-toluene measured in a wide temperature range above and below the melting point. The nature of the electron spin coherence phase memory is investigated. The properties of all resonance lines in a liquid phase were treated within the model of the free rotational diffusion. Both, analytical expressions and numerical examination provide an excellent agreement between the experimental and simulated spectra. A detailed study of the experimental data confirms the assumption of the independent motions of the fullerene cage and the Sc2 core. The data obtained show three regimes of molecular motion detected at different temperatures: the free rotation of both the fullerene cage and its bi-metal core, the motion of the core in the frozen fullerene cage, and, finally, a state with a fixed structure of both parts of the metallofullerene molecules. The data analysis reveals a significant nuclear quadrupole interaction playing an important role for the mixing of the different nuclear spin multiplets.

Terahertz Magneto-Optical Excitations of the sd-Hybrid States of Lithium Nitridocobaltate Li2(Li1-xCox)N.

We report the results of the experimental and theoretical study of the magnetic anisotropy of single crystals of the Co-doped lithium nitride Li2(Li1-xCox)N with x = 0.005, 0.01, and 0.02. It was shown recently that doping of the Li3N crystalline matrix with 3d transition metal (TM) ions yields superior magnetic properties comparable with the strongly anisotropic single-molecule magnetism of rare-earth complexes. Our combined electron spin resonance (ESR) and THz spectroscopic investigations of Li2(Li1-xCox)N in a very broad frequency range up to 1.7 THz and in magnetic fields up to 16 T enable an accurate determination of the energies of the spin levels of the ground state multiplet Ŝ = 1 of the paramagnetic Co(I) ion. In particular, we find a very large zero field splitting (ZFS) of almost 1 THz (∼4 meV or 33 cm-1) between the ground-state singlet and the first excited doublet state. On the computational side, ab initio many-body quantum chemistry calculations reveal a ZFS gap consistent with the experimental value. Such a large ZFS energy yields a very strong single-ion magnetic anisotropy of easy-plane type resembling that of rare-earth ions. Its microscopic origin is the unusual linear coordination of the Co(I) ions in Li2(Li1-xCox)N with two nitrogen ligands. Our calculations also evidence a strong 3d-4s hybridization of the electronic shells resulting in significant electron spin density at the 59Co nuclei, which may be responsible for the experimentally observed extraordinary large hyperfine structure of the ESR signals. Altogether, our experimental spectroscopic and computational results enable comprehensive insights into the remarkable properties of the Li2[Li1-x(TM)x]N magnets on the microscopic level.

Unusually large hyperfine structure of the electron spin levels in an endohedral dimetallofullerene and its spin coherent properties.

We report the synthesis, ESR spectroscopic and spin coherent properties of the dimetallofullerene Sc2@C80(CH2Ph). The single-electron metal-metal bond of the Sc2 dimer inside the fullerene's cage is stabilized with the electron spin density being fully localized at the metal bond. This results in an extraordinary strong hyperfine interaction of the electron spin with the 45Sc nuclear spins with a coupling constant a = 18.2 mT (∼510 MHz) and yields a fully resolved hyperfine-split ESR spectrum comprising 64 lines. The splitting is present even at low temperatures where the molecular dynamics are completely frozen. The large extent and the robustness of the hyperfine-split spectra enable us to identify and control the well-defined transitions between specific electron-nuclear quantum states. This made it possible to demonstrate in our pulse ESR study the remarkable spin coherent dynamics of Sc2@C80(CH2Ph), such as the generation of arbitrary superpositions of the spin states in a nutation experiment and the spin dephasing times above 10 µs at temperatures T < 80 K reaching the value of 17 µs at T ≤ 20 K. These observations suggest Sc2@C80(CH2Ph) as an interesting qubit candidate and motivate further synthetic efforts to obtain fullerene-based systems with superior spin properties.

An unusual donor-acceptor system MnIIPc-TCNQ/F4-TCNQ and the properties of the mixed single crystals of metal phthalocyanines with organic acceptor molecules.

The interaction of manganese(ii) phthalocyanine with 7,7,8,8-tetracyanoquinodimethane and its perfluoro derivative proceeds with the oxidation of Mn and the reduction of the acceptor molecules to give the first mixed single crystals of manganese(iii) phthalocyanine with TCNQ/F4-TCNQ radical anions. The crystals have unusual structures with C-Hπ interactions between the ions and their orthogonal arrangement, as well as remarkable redox properties. The charge transfer was proved by spectroscopic and magnetic studies.

Effect of the Diamagnetic Single-Crystalline Host on the Angular-Resolved Electron Nuclear Double Resonance Experiments: Case of Paramagnetic [nBu4N]2[Cu(opba)] Embedded in Diamagnetic [nBu4N]2[Ni(opba)].

The electron spin resonance (ESR) and electron nuclear double resonance (ENDOR) spectroscopies are frequently used to determine hyperfine (A) and quadrupole (Q) tensors for the paramagnetic transition-metal complexes, which knowledge enables estimation of the spin density distribution in the complex and the assessment of magnetic exchange pathways in polynuclear molecular networks. The most accurate results can be obtained if paramagnetic complexes are isolated in a single-crystalline diamagnetic host. In this work we were able to detect angle-resolved ESR/ENDOR spectra of the paramagnetic [nBu4N]2[Cu(opba)] (opba = o-phenylenebis(oxamato) complex hosted by the single crystal of diamagnetic [nBu4N]2[Ni(opba)], which allow recovery of A, Q, and g-tensors, all at once. Remarkably, with the aid of theoretical modeling, our data have unveiled the effect of multipositional hosting of the paramagnetic complex in the diamagnetic matrix. This effect can have a profound influence on the data handling and must be carefully considered while interpreting similar experiments.

Superconducting switching due to a triplet component in the Pb/Cu/Ni/Cu/Co2Cr1 -x Fe x Al y spin-valve structure.

We report the superconducting properties of the Co2Cr1 -x Fe x Al y /Cu/Ni/Cu/Pb spin-valve structure the magnetic part of which comprises the Heusler alloy layer HA = Co2Cr1 -x Fe x Al y with a high degree of spin polarization (DSP) of the conduction band and a Ni layer of variable thickness. The separation between the superconducting transition curves measured for the parallel (α = 0°) and perpendicular (α = 90°) orientation of the magnetization of the HA and the Ni layers reaches up to 0.5 K (α is the angle between the magnetization of two ferromagnetic layers). For all studied samples the dependence of the superconducting transition temperature T c on α demonstrates a deep minimum in the vicinity of the perpendicular configuration of the magnetizations. This suggests that the observed minimum and the corresponding full switching effect of the spin valve is caused by the long-range triplet component of the superconducting condensate in the multilayer. Such a large effect can be attributed to a half-metallic nature of the HA layer, which in the orthogonal configuration efficiently draws off the spin-polarized Cooper pairs from the space between the HA and Ni layers. Our results indicate a significant potential of the concept of a superconducting spin-valve multilayer comprising a half-metallic ferromagnet, recently proposed by A. Singh et al., Phys. Rev. X 2015, 5, 021019, in achieving large values of the switching effect.

A Phthalocyanine-Based Layered Two-Dimensional Conjugated Metal-Organic Framework as a Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction.

Layered two-dimensional (2D) conjugated metal-organic frameworks (MOFs) represent a family of rising electrocatalysts for the oxygen reduction reaction (ORR), due to the controllable architectures, excellent electrical conductivity, and highly exposed well-defined molecular active sites. Herein, we report a copper phthalocyanine based 2D conjugated MOF with square-planar cobalt bis(dihydroxy) complexes (Co-O4 ) as linkages (PcCu-O8 -Co) and layer-stacked structures prepared via solvothermal synthesis. PcCu-O8 -Co 2D MOF mixed with carbon nanotubes exhibits excellent electrocatalytic ORR activity (E1/2 =0.83 V vs. RHE, n=3.93, and jL =5.3 mA cm-2 ) in alkaline media, which is the record value among the reported intrinsic MOF electrocatalysts. Supported by in situ Raman spectro-electrochemistry and theoretical modeling as well as contrast catalytic tests, we identified the cobalt nodes as ORR active sites. Furthermore, when employed as a cathode electrocatalyst for zinc-air batteries, PcCu-O8 -Co delivers a maximum power density of 94 mW cm-2 , outperforming the state-of-the-art Pt/C electrocatalysts (78.3 mW cm-2 ).

Zn and Co redox active coordination polymers as efficient electrocatalysts.

New redox active 1D helical coordination polymers M(fcdHp) (M(ii) = Zn(1), Co(2)) have been obtained by utilizing the 1,1'-ferrocenylenbis(H-phosphinic) acid (H2fcdHp) ligand and Zn or Co nitrate salts. Complexes 1 and 2 are isomorphic, crystallizing in the chiral space groups P4122 and P4322, respectively. Their redox, electrocatalytic and other properties are described. These compounds incorporated into carbon paste electrodes and exhibited reversible redox reactions, arising from the ferrocenyl moiety. These coordination polymers are efficient as electrocatalysts for the reduction of protons to hydrogen. Using N,N-dimethylformamidium ([DMF(H)+]) as the acid in the acetonitrile solution, Co CP (2) displays a turnover frequency of 300 s-1, which is among the fastest rates reported for any CP electrocatalyst in CH3CN. This high rate of catalytic reaction comes at the cost of the 820-840 mV overpotential at the potential of catalysis. As the hydrogen evolution reaction (HER) catalysts, the CPs exhibited in 0.5 M H2SO4 the overpotential η10 of 340 or 450 mV, onset overpotential of 220 or 300 mV (vs. RHE), Tafel slope of 110 or 120 mV dec-1, correspondingly for 1 and 2, and considerable long-term stability for the HER.

Increasing the performance of a superconducting spin valve using a Heusler alloy.

We have studied superconducting properties of spin-valve thin-layer heterostructures CoO x /F1/Cu/F2/Cu/Pb in which the ferromagnetic F1 layer was made of Permalloy while for the F2 layer we have taken a specially prepared film of the Heusler alloy Co2Cr1-x Fe x Al with a small degree of spin polarization of the conduction band. The heterostructures demonstrate a significant superconducting spin-valve effect, i.e., a complete switching on and off of the superconducting current flowing through the system by manipulating the mutual orientations of the magnetization of the F1 and F2 layers. The magnitude of the effect is doubled in comparison with the previously studied analogous multilayers with the F2 layer made of the strong ferromagnet Fe. Theoretical analysis shows that a drastic enhancement of the switching effect is due to a smaller exchange field in the heterostructure coming from the Heusler film as compared to Fe. This enables to approach an almost ideal theoretical magnitude of the switching in the Heusler-based multilayer with a F2 layer thickness of ca. 1 nm.

The interplay between spin densities and magnetic superexchange interactions: case studies of mono- and trinuclear bis(oxamato)-type complexes.

For future molecular spintronic applications the possibility to modify and tailor the magnetic properties of transition-metal complexes is very promising. One of such possibilities is given by the countless derivatization offered by carbon chemistry. They allow for altering chemical structures and, in doing so, to tune magnetic properties of molecular spin-carrying compounds. With emphasis on the interplay of the spin density distribution of mononuclear and magnetic superexchange couplings of trinuclear bis(oxamato)-type complexes we review on efforts on such magneto-structural correlations.

Static and dynamic magnetic properties of the ferromagnetic coordination polymer [Co(NCS)2(py)2]n.

[Co(NCS)2(py)2]n (py = pyridine) is composed of ferromagnetic chains of Co(ii) cations connected by double NCS bridges. The chains are irregular because of two crystallographically inequivalent Co(ii) cations. The coordination polyhedron of the Co(ii) cations is a distorted octahedron built from two N and two S atoms of four equatorial NCS anions and two apical N atoms of the pyridine ligands. Magnetic and specific heat studies show that the compound undergoes a phase transition at 3.7 K to a ferromagnetic state. The determined magnetic interactions, intrachain (J/kB = 28 K) and interchain (zJ'/kB = 0.5 K), confirm the quasi 1D Ising magnetic character of [Co(NCS)2(py)2]n. Using AC magnetic susceptibility measurements the energy barriers for magnetization reversal of different relaxation processes were determined including those of the individual chains. By means of high field-high frequency ESR study the magnetic excitations were observed and explained in the frame of the Ising model in agreement with the results of the magnetic study. Ab initio calculations confirm the high magnetic anisotropy of the system and allow determination of the direction of the easy-axis. The broken symmetry DFT calculations support the ferromagnetic intrachain interactions. The energetic relations relevant for relaxations are discussed. It is concluded that the magnetic model of [Co(NCS)2(py)2]n is not a pure Ising but the transversal exchange plays a role.

Probing the magnetic superexchange couplings between terminal CuII ions in heterotrinuclear bis(oxamidato) type complexes.

The reaction of one equivalent of [n-Bu4N]2[Ni(opboR2)] with two equivalents of [Cu(pmdta)(X)2] afforded the heterotrinuclear CuIINiIICuII containing bis(oxamidato) type complexes [Cu2Ni(opboR2)(pmdta)2]X2 (R = Me, X = NO3- (1); R = Et, X = ClO4- (2); R = n-Pr, X = NO3- (3); opboR2 = o-phenylenebis(NR-substituted oxamidato); pmdta = N,N,N',N",N"-pentamethyldiethylenetriamine). The identities of the heterotrinuclear complexes 1-3 were established by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction studies, which revealed the cationic complex fragments [Cu2Ni(opboR2)(pmdta)2]2+ as not involved in any further intermolecular interactions. As a consequence thereof, the complexes 1-3 possess terminal paramagnetic [Cu(pmdta)]2+ fragments separated by [NiII(opboR2)]2- bridging units representing diamagnetic SNi = 0 states. The magnetic field dependence of the magnetization M(H) of 1-3 at T = 1.8 K has been determined and is shown to be highly reproducible with the Brillouin function for an ideal paramagnetic spin = 1/2 system, verifying experimentally that no magnetic superexchange couplings exists between the terminal paramagnetic [Cu(pmdta)]2+ fragments. Susceptibility measurements versus temperature of 1-3 between 1.8-300 K were performed to reinforce the statement of the absence of magnetic superexchange couplings in these three heterotrinuclear complexes.

Tuning the spin coherence time of Cu(II)-(bis)oxamato and Cu(II)-(bis)oxamidato complexes by advanced ESR pulse protocols.

We have investigated with the pulsed ESR technique at X- and Q-band frequencies the coherence and relaxation of Cu spins S = 1/2 in single crystals of diamagnetically diluted mononuclear [n-Bu4N]2[Cu(opba)] (1%) in the host lattice of [n-Bu4N]2[Ni(opba)] (99%, opba = o-phenylenebis(oxamato)) and of diamagnetically diluted mononuclear [n-Bu4N]2[Cu(opbon-Pr2)] (1%) in the host lattice of [n-Bu4N]2[Ni(opbon-Pr2)] (99%, opbon-Pr2 = o-phenylenebis(N(propyl)oxamidato)). For that we have measured the electron spin dephasing time Tm at different temperatures with the two-pulse primary echo and with the special Carr-Purcell-Meiboom-Gill (CPMG) multiple microwave pulse sequence. Application of the CPMG protocol has led to a substantial increase of the spin coherence lifetime in both complexes as compared to the primary echo results. It shows the efficiency of the suppression of the electron spin decoherence channel in the studied complexes arising due to spectral diffusion induced by a random modulation of the hyperfine interaction with the nuclear spins. We argue that this method can be used as a test for the relevance of the spectral diffusion for the electron spin decoherence. Our results have revealed a prominent role of the opba4- and opbon-Pr24- ligands for the dephasing of the Cu spins. The presence of additional 14N nuclei and protons in [Cu(opbon-Pr2)]2- as compared to [Cu(opba)]2- yields significantly shorter Tm times. Such a detrimental effect of the opbon-Pr24- ligands has to be considered when discussing a potential application of the Cu(II)-(bis)oxamato and Cu(II)-(bis)oxamidato complexes as building blocks of more complex molecular structures in prototype spintronic devices. Furthermore, in our work we propose an improved CPMG pulse protocol that enables elimination of unwanted echoes that inevitably appear in the case of inhomogeneously broadened ESR spectra due to the selective excitation of electron spins.

Aligned cuboid iron nanoparticles by epitaxial electrodeposition.

Aligned, individual iron square cuboid nanoparticles have been achieved by taking advantage of epitaxial, three-dimensional-island growth on GaAs(001) during electrodeposition at low deposition rates. The nanoparticles exhibit lateral dimensions between 10 and 80 nm and heights below 40 nm. Surface {100} facets predominate with a thin crystalline oxide shell that protects the nanoparticles during prolonged storage in air. The single crystallinity of the iron in combination with structural alignment leads to an in-plane magnetic anisotropy. These immobilized, oriented, and stable nanoparticles are promising for applications in nanoelectronic, sensor, and data storage technologies, as well as for the detailed analysis of the effect of shape and size on magnetism at the nanoscale.

NiII formate complexes with bi- and tridentate nitrogen-donor ligands: synthesis, characterization, and magnetic and thermal properties.

The synthesis of four NiII formate complexes of the type [Ni(N∩N)n][O2CH]2 (2, adduct with 3/4 EtOH, N∩N = en, e[combining low line]thylen[combining low line]ediamine, n = 3; 4, N∩N = dien, N,N',N''-d[combining low line]i[combining low line]e[combining low line]thylen[combining low line]etriamine, n = 2), [Ni2(O2CH)4(H2O)(tmeda)2] (3, tmeda = N,N,N',N'-t[combining low line]etram[combining low line]ethyle[combining low line]thylened[combining low line]ia[combining low line]mine) and [{Ni(O2CH)2(pmdta)}2·H2O] (5, pmdta = N,N',N',N'',N''-p[combining low line]entam[combining low line]ethyld[combining low line]iethylenet[combining low line]ria[combining low line]mine) by a reaction of [{Ni(O2CH)2}·2H2O] (1) with the respective N-donor bases is reported. The structures of 2-5 in the solid state were determined by single X-ray structure analysis, revealing a discrete dinuclear structure of 3 and the formation of polymeric networks in the case of 2, 4 and 5 due to intermolecular hydrogen bonding. SQUID and ESR measurements of 3 evidenced a weak antiferromagnetic coupling between the NiII ions and an easy plane magnetic anisotropy. Accompanying quantum chemical studies of the magnetic properties and IR characteristics of 3 were performed to strengthen the conclusions drawn from experimentally obtained data. The thermal decomposition temperatures of 2-5 were determined by TG (thermogravimetry) and obtained residues were analyzed by PXRD (powder X-ray diffraction) measurements. The decomposition processes were completed at 207 (3), 215 (5), 250 (2) and 273 °C (4) and are shown to result in the formation of pure metallic nickel.

A Three-Pronged Attack To Investigate the Electronic Structure of a Family of Ferromagnetic Fe4Ln2 Cyclic Coordination Clusters: A Combined Magnetic Susceptibility, High-Field/High-Frequency Electron Paramagnetic Resonance, and 57Fe Mössbauer Study.

We present the synthesis, structure, magnetic properties, as well as the Mössbauer and electron paramagnetic resonance studies of a ring-shaped [FeIII4LnIII2(Htea)4(µ-N3)4(N3)3(piv)3] (Ln = Y 1, Gd 2, Tb 3, Dy 4, Ho 5, Er, 6) coordination cluster. The Dy, Tb, and Ho analogues show blocking of the magnetization at low temperatures without applied fields. The anisotropy of the 3d ion and the exchange interaction between 3d and 4f ions in Fe4Ln2 complexes are unambiguously determined by high-field/high-frequency electron paramagnetic resonance measurements at low temperature. Ferromagnetic exchange interaction JFe-Ln is found which decreases upon variation of the Ln ions to larger atomic numbers. This dependence is similar to the behavior shown in the effective barrier values of complexes 3-5. Further information about the anisotropy of the Ln3+ ions was gathered with 57Fe Mössbauer spectroscopy, and the combination of these methods provides detailed information regarding the electronic structure of these complexes.