Experimental Magnetic Data Research Articles

Pyridyl-Substituted Nitronyl Nitroxides: Comprehensive Magnetochemical and Quantum Chemical Study.

A series of pyridyl-substituted nitronyl nitroxides was synthesized and structurally characterized. A comprehensive magnetochemical and quantum chemical study of extended raw of the nitroxides with different substituents R in the pyridine fragment was performed. It was shown, that temperature-dependent magnetic properties are determined by the short contacts between nitroxide groups of adjacent molecules as well as between nitroxide group and methyl substituents in the pseudo axial positions of imidazoline fragments. Quantum chemistry allows to select the appropriate model of exchange cluster for analysis of experimental magnetic data and evaluation of the exchange interaction parameters. For NN-PyCl the "order-disorder" transition was detected by means of low temperature XRD. The difference in the experimental and calculated exchange interaction energies may serve as an indicator of temperature-induced structural rearrangements. For instance, for methyl substituted nitronyl nitroxide NN-PyMe structural transformations and significant changes in exchange interaction energies were observed.

The alloyed cementite (Fe–Ni–Cr)3C: Local environment, atomic magnetic moments, and magnetization from DFT calculation

The alloying element added to carbon steel to enhance its properties also penetrates Fe3C cementite particles, altering their properties and influencing the steel product through them. This is why the impact of alloying elements on cementite has been extensively studied. Ni and Cr exhibit opposing behavior in cementite, so cementite doped with Ni and Cr is investigated using DFT calculations. The data obtained for total energy, lattice, magnetization, local magnetic moments at metal atoms, and their nearest environment are compared to experimental magnetic data for Ni and Cr-alloyed cementite. The relationship between Fe atom magnetic moments and their nearest environment is discussed in comparison between Cr and Ni doping. Decrease in magnetization with Ni and Cr content is attributed to 1) replacement of a larger Fe magnetic moment (mFe = 1.9–2.0 μB) with a smaller or even negative moment (mNi = 0.2–0.5 μB, mCr = −0.3 to −1.0 μB); 2) a decrease in the average Fe moment with the number of Cr atoms in the nearest environment; and 3) a strong dependence of the Curie temperature on Cr content in Cr-doped cementite.

Intertwined crystal structure, magnetic, and charge transport properties in mixed valent A-site ordered manganite NdBaMn2O6

In the present work, we report a correlation between crystal structure, magnetic, and electrical properties in an exotic magnetic compound, NdBaMn2O6 having ∼92% ordering between Nd and Ba, investigated using temperature-dependent synchrotron x-ray diffraction (XRD), dc magnetization and transport measurements. Temperature-dependent XRD data reveals that the compound undergoes various complex crystallographic phase transitions from high-temperature (T > 320 K) P4/mmm phase to intermediate (320 K – 280 K) Cmmm phase to a mixed (Cmmm and P21am) phase (280 K – 220 K) and to low-temperature P21am phase (T < 220 K). It is found that these crystallographic phase compositions play a crucial role in controlling its magnetic and transport properties. Temperature-dependent dc magnetization data show a sharp drop at the onset of mixed phase (Cmmm + P21am) at 280 K followed by a broad hump at ∼ 220 K where mixed phase to P21am transition occurs, thus indicating a correlation between the structural and magnetic properties. The dc magnetization in the mixed phase region is calculated by considering a superposition of the magnetic moments of Cmmm and P21am phases weighted by the fraction of each phase, which exactly follows the experimental magnetization data. Temperature variation of resistivity data shows a jump at ∼260 K, a temperature corresponding to 50–50% phase composition of Cmmm and P21am phases. The compound shows insulating behavior over a whole temperature range as confirmed from the resistivity data. Further, application of magnetic field causes a shift of magnetic and transport transition temperatures which may be due to the magnetic field induced structural transition in the system.

Low-temperature magnetocaloric effect of the polyoxovanadate molecular magnet {VIV/V12As8}: An experimental study

Magnetic measurements have been performed for the compound (NH(C2H5)3)4[VIV8VV4AsIII8 O40(H2O)]·H2O compound in order to determine its magnetocaloric effect in terms of the isothermal entropy change and compare it to the theoretical prediction based on the previously developed model. A closer inspection of the experimental magnetization and susceptibility data revealed that this model is incomplete neglecting a contribution from the off-center V4 subsystems, where the vanadium ions are in the mixed valence state. The probability that two valence electrons residing within the two off-center V4 subsystems are magnetically decoupled was estimated to be equal to 2 – 3 %. For most of the time they turn out to be magnetically correlated by the high antiferromagnetic superexchange interaction. The magnetocaloric effect calculated with the full model accounting for the off-center contribution was found to agree satisfactorily with the values derived from the measured magnetization data. A valuable byproduct of the analysis is the rigorous estimation of the errors in the isothermal entropy change due to the necessary numerical approximations.

New series of mononuclear β-diketonate cerium(III) field induced single-molecule magnets.

Five new β-diketonate Ce3+ mononuclear complexes, [Ce(Btfa)3(H2O)2] (1), [Ce(Btfa)3(phen)] (2), [Ce(Btfa)3(bipy)] (3), [Ce(Btfa)3(terpy)] (4) and [Ce(Btfa)3(bathophen)(DMF)] (5), where Btfa- = 4,4,4-trifluoro-1-phenyl-1,3-butanedionate, phen = 1,10-phenanthroline, bipy = 2,2'-bipyridyl, terpy = 2,2':6',2''-terpyridine and bathophen = 4,7-diphenyl-1,10-phenanthroline, have been synthesized and structurally characterized through X-ray diffraction of single crystals. The central Ce3+ atom displays a coordination number of 8 for 1, 2 and 3 and of 9 for 4 and 5. Under a 0 T external magnetic field, none of the given compounds exhibits single molecule magnet (SMM) behaviour. However, a small magnetic field, between 0.02 and 0.1 T, is enough for all the compounds to exhibit slow relaxation of the magnetization. A comprehensive magnetic analysis, with experimental magnetic data and ab initio calculations, was undertaken for all the complexes, and the study highlights the significance of the different spin relaxation mechanisms that must be considered for a Ce3+ lanthanide ion.

Research on temperature rise characteristics and hot spot temperature inversion method of oil-immersed transformer based on coupling of magnetic-fluid-thermal field

The hot spot temperature is an important factor affecting the operation state and insulation life of oil-immersed transformer. It is of great value to carry out multi-physical field coupling simulation research on magnetic-fluid-thermal field of oil-immersed transformer and accurately calculate and predict the hot spot temperature of transformer for transformer service life evaluation. In this paper, the oil immersed transformer is taken as the research object, and five characteristic parameters of the hysteresis model are obtained by using PSO optimization algorithm according to the experimental magnetic characteristics data of the core material and the classical J-A hysteresis model, A 3D simulation model of magnetic-fluid-thermal field is established based on the electrical and structural parameters of the oil-immersed transformer. Combined with the magnetic characteristics of the core material, the thermal field and the surrounding fluid distribution of the transformer core and winding are obtained by two-way coupling method. On this basis, in order to accurately reflect the correlation between the hot spot temperature of the transformer winding and the temperature of the oil tank wall, the selection position of the characteristic temperature point of the transformer tank wall is determined by streamline analysis method, and the hot spot temperature of the oil-immersed transformer is retrieved by support vector machine method. The results show that the prediction accuracy of the hot spot temperature reaches 0.998, and the inversion method has a high enough accuracy. It provides theoretical basis and technical support for real-time monitoring of hot spot temperature in oil-immersed transformer windings.

Magnetic study and DFT analysis of a doubly carboxylato-bridged Co(II) derivative anchored with a 'scorpionate' precursor as a potential electrocatalyst for heterogeneous H2 evolution.

A new doubly carboxylato-bridged Co(II) dinuclear complex, [Co(bdtbpza)(NCS)]2 (1), was obtained in a satisfactory yield by employing a 'scorpionate'-type precursor, bdtbpza {bis-(3,5-di-tert-butylpyrazol-1-yl)acetate}, and was then structurally characterized. Single-crystal X-ray diffraction analysis revealed that, in 1, each Co(II) is penta-coordinated, leading to a distorted trigonal-bipyramidal geometry within the coordination environment of N3O2. Weak antiferromagnetic coupling within the Co(II) ions in 1 was found based on the isotropic spin Hamiltonian H = -J(S1·S2) for the Si = 3/2 system. For evaluating the spin density distribution and the mechanism for the magnetic exchange coupling, DFT analysis was performed, with the calculated result agreeing the experimental magnetic data. A study into electrochemical H2 evolution, involving cyclic voltammetry (CV), controlled potential electrolysis (CPE), and gas chromatographic (GC) analyses of the graphite electrode modified with the cobalt complex in a neutral aqueous solution revealed the high catalytic activity of the complex with a low overpotential toward H2O reduction. The faradaic efficiency of the catalyst was found to be 83.7% and the di-cobalt catalyst-modified electrode displayed quite an interesting H2-evolution activity compared with that of bare electrodes. These results are encouraging for the future potential application of 1 in water splitting.

Spin Symmetry in Polynuclear Exchange-Coupled Clusters

The involvement of spin symmetry in the evaluation of zero-field energy levels in polynuclear transition metal and lanthanide complexes facilitates the division of the large-scale Hamiltonian matrix referring to isotropic exchange. This method is based on the use of an irreducible tensor approach. This allows for the fitting of the experimental data of magnetic susceptibility and magnetization in a reasonable time for relatively large clusters for any coupling path. Several examples represented by catena-[AN} and cyclo-[AN] systems were modeled. Magnetic data for 20 actually existing endohedral clusters were analyzed and interpreted.

Mn(III)–Salen Complexes with Metallophilic Interactions

We synthesized a series of five novel Mn–salen-based compounds (1a–1c, 2a, 2b) through the reaction between precursor chloride complexes and potassium silver/gold dicyanide. The prepared compounds were structurally and magnetically characterized. Our findings revealed that all the Mn(III) central atoms exhibited an axially elongated coordination polyhedron, leading to the observation of axial magnetic anisotropy as indicated by the negative axial magnetic parameter D, which was determined through fitting the experimental magnetic data and supported by theoretical CASSCF/NEVPT2 calculations. Furthermore, we observed magnetic-exchange interactions only in compounds with a special supramolecular topology involving O–H···O hydrogen-bonded dimers. In these cases, the weak magnetic exchange (J/cm−1 = −0.58(2) in 1b and −0.73(7) in 2b) was mediated by the O–H···O hydrogen bonds. These findings were further supported by BS–DFT calculations, which predicted weak antiferromagnetic exchanges in these complexes and ruled out exchange interactions mediated by diamagnetic cyanido metallo–complex bridges. Additionally, we investigated the observed Ag···π (1b) and Au···Au (2b) interactions using QT–AIM calculations, confirming their non-covalent nature. We compared these results with previously reported Mn–salen-based compounds with metallophilic interactions arising from the presence of the [Ag/Au(CN)2]− bridging units.

Estimating the Net Magnetic Moment of Geological Samples From Planar Field Maps Using Multipoles

AbstractRecent advances in magnetic microscopy have enabled studies of geological samples whose weak and spatially nonuniform magnetizations were previously inaccessible to standard magnetometry techniques. A quantity of central importance is the net magnetic moment, which reflects the mean direction and the intensity of the magnetization states of numerous ferromagnetic crystals within a certain volume. The planar arrangement of typical magnetic microscopy measurements, which originates from measuring the field immediately above the polished surface of a sample to maximize sensitivity and spatial resolution, makes estimating net moments considerably more challenging than with spherically distributed data. In particular, spatially extended and nonuniform magnetization distributions often cannot be adequately approximated by a single magnetic dipole. To address this limitation, we developed a multipole fitting technique that can accurately estimate net moment using spherical harmonic multipole expansions computed from planar data. Given that the optimal location for the origin of such expansions is unknown beforehand and generally unconstrained, regularization of this inverse problem is critical for obtaining accurate moment estimates from noisy experimental magnetic data. We characterized the performance of the technique using synthetic sources under different conditions (noiseless data, data corrupted with simulated white noise, and data corrupted with measured instrument noise). We then validated and demonstrated the technique using superconducting quantum interference device microscopy measurements of impact melt spherules from Lonar crater, India and dusty olivine chondrules from the CO chondrite meteorite Dominion Range 08006.

Characterization of Terfenol-D and Comparison With Predictions of a Thermodynamically Consistent Two-Input, Two-Output Model of Hysteresis

Since its discovery more than forty years ago, Terfenol-D has promised much but has not yet been fully exploited in applications.The main reason for this is that it shows significant hysteresis and other nonlinearities, such as saturation, which need to be modeled correctly in order to maximize the application potential. In this article, we focus on the characterization of a Terfenol-D sample with the intention of developing a predictive two-input (magnetic field and stress) and two-output (magnetic flux density and strain) model of magnetostriction that exhibits hysteresis and saturation and is compatible with the laws of thermodynamics. Compatibility with thermodynamics is essential to ensure that numerical simulations do not exhibit unphysical behavior. The model is based on the Preisach hysteresis operator and its storage function and may be interpreted as a two-input, two-output neural net with elementary hysteresis operators as the neurons. In order to estimate the parameters, it is necessary to collect data over a wide range of magnetic fields (-300 kA/m to 300 kA/m) and compressive stresses (up to 60 MPa). Using the rate-independent memory evolution properties of the Preisach operator, we split the parameter estimation problem into three numerically well-conditioned, linear least squares problems with constraints. We show that the model is able to fit experimental data for strain and magnetization over a wide range of magnetic fields and stress.

Lipoic Acid-Functionalized Hexanuclear Manganese(III) Nanomagnets Suitable for Surface Grafting.

Highly anisotropic single-molecule magnets (SMMs) have attracted much interest in the field of molecular magnetism because of their spin features and potential technological applications. Additionally, a great effort has been devoted to the functionalization of such molecule-based systems which are made with ligands containing functional groups suitable to connect SMMs to junction devices or to perform their grafting on surfaces of different substrates. We have synthesized and characterized two lipoic acid-functionalized and oxime-based Mn(III) compounds, of formula [Mn6(μ3-O)2(H2N-sao)6(lip)2(MeOH)6][Mn6(μ3-O)2(H2N-sao)6(cnph)2(MeOH)6]}·10MeOH (1) and [Mn6(μ3-O)2(H2N-sao)6(lip)2(EtOH)6]·EtOH·2H2O (2) [H2N-saoH2 = salicylamidoxime, lip = lipoate anion, cnph = 2-cyanophenolate anion]. Compound 1 crystallizes in the space group Pī of the triclinic system and 2 crystallizes in the space group C2/c of the monoclinic system. In the crystal, neighboring Mn6 entities are linked using non-coordinating solvent molecules, which are H-bonded to N atoms of -NH2 groups of amidoxime ligand. In addition, Hirshfeld surfaces of 1 and 2 were calculated to study the variety of intermolecular interactions and the different levels of importance that take place in their crystal lattice; this type of computed study is the first time performed on Mn6 complexes. The study of the magnetic properties of 1 and 2 through dc magnetic susceptibility measurements reveals the coexistence of ferromagnetic and antiferromagnetic exchange couplings between the Mn(III) metal ions in both compounds, the latter being the predominant magnetic interaction. A spin S = 4 value of the ground state was obtained using isotropic simulations of the experimental magnetic susceptibility data for both 1 and 2. Ac magnetic susceptibility measurements show features typical of slow relaxation of the magnetization in 1 and 2, which indicate that SMM behavior takes place in both compounds.

Parameter identification for a model for multi-functional materials with hysteresis and thermodynamic compatibility

Multifunctional materials have tremendous potential for engineering applications as they are able to convert mechanical to electromagnetic energy and vice-versa. One of the features of this class of materials is that they show significant hysteresis, which needs to be modeled correctly in order to maximize their application potential. A method of modeling multifunctional materials that exhibit the phenomenon of hysteresis and is compatible with the laws of thermodynamics was developed recently. The model is based on the Preisach hysteresis operator and its storage function and may be interpreted as a two-input, two-output neural net with elementary hysteresis operators as the neurons. The difficulty is that the parameters in the model appear in a non-linear fashion, and there are several constraints that must be satisfied by the parameters for thermodynamic compatibility. In this article, we present a novel methodology that uses the rate-independent memory evolution properties of the Preisach operator to split the parameter estimation problem into three numerically well-conditioned, linear least squares problems with constraints. The alternative direction method of multipliers (ADMM) algorithm and accelerated proximal gradient method are used to compute the Preisach weights. Numerical results are presented over data collected from experiments on a Galfenol sample. We show that the model is able to fit not only experimental data for strain and magnetization over a wide range of magnetic fields and stress but also able to predict the response for stress and magnetic fields not used in the parameter estimation.

Fe-Gd Ferromagnetic Cyclic Coordination Cluster [FeIII4GdIII4(teaH)8(N3)8(H2O)] with Magnetic Anisotropy─Theory and Experiment.

The synthesis, structural, and magnetic characterization of [FeIII4LnIII4(teaH)8(N3)8(H2O)] (Ln = Gd and Y) and the previously reported isostructural Dy analogue are discussed. The commonly held belief that both FeIII and GdIII can be regarded as isotropic ions is shown to be an oversimplification. This conclusion is derived from the magnetic data for the YIII analogue in terms of the zero-field splitting seen for FeIII and from the fact that the magnetic data for the new GdIII analogue can only be fit employing an additional anisotropy term for the GdIII ions. Furthermore, the Fe4Gd4 ring shows slow relaxation of magnetization. Our analysis of the experimental magnetic data employs both density functional theory as well as the finite-temperature Lanczos method which finally enables us to provide an almost perfect fit of magnetocaloric properties.

Landau theory-based relaxational modeling of first-order magnetic transition dynamics in magnetocaloric materials

The magnetocaloric effect is often largest within the neighborhood of a first-order phase transition. This effect can be utilized in magnetocaloric refrigeration, which completely eliminates the need for the greenhouse gases utilized in conventional refrigeration. However, such transitions present unique dynamical effects and are accompanied by hysteresis, which can be detrimental for such refrigeration applications. In this work, a Landau theory-based relaxational model is used to study the magnetic hysteresis and dynamics of the first-order magnetic transition of LaFe13−x Si x . Fitting the experimental magnetization data as a function of applied magnetic field under different field sweep rates with this model provided the Landau parameters (A, B, and C) and the kinetic coefficient of the studied material. We demonstrate the tendency of the magnetic hysteresis to increase with the magnetic field sweep rate, underlining the importance of studying and minimizing the magnetic hysteresis in magnetic refrigerants at practical field sweep rates. While evaluating the temperature dependence of the time required for a complete transition to occur, a nonmonotonic behavior and a sharp peak were found for temperatures near the transition temperature. Such peaks occur at the same temperature as the peak of the magnetic entropy change for low fields, whereas for higher fields the two peaks decouple. This information is critical for technological applications (such as refrigerators/heat pumps) as it provides guidelines for the optimization of the magnetic field amplitude in order to reduce the transition timescale and consequently maximize the machine operational frequency and amount of heat that is pumped in/out per second.

Ferromagnetism and dielectric properties in Zn0.95−xNdxTM0.05O (TM=Co, Fe) nanocrystals: Collective role of grain boundaries and oxygen vacancies

Herein, Zn0.95−xNdxTM0.05O (TM = Co, Fe) (x = 2%, 6%) nanocrystals with spherical shape, wurtzite-like hexagonal structure, and average crystallite size of 35 nm were prepared by sol-gel method, those exhibit ferromagnetic (FM) behavior at room temperature. X-ray photoelectron spectroscopy (XPS) results confirmed the successful incorporation of dopants ions such as Nd3+ and Co2+/Fe2+ into the host ZnO lattice. Size-strain analysis based on the Williamson-Hall plot was performed to evaluate the crystallite size and lattice strain. High-resolution transmission electron microscope characterization shows that the fine nanocrystals are separated by grain boundaries (GBs). The calculated specific grain boundary area (SGB) of 60 × 106m2m-3 in the co-doped samples is above the threshold value of 5.3 × 107 m2m-3. The UV–Visible analysis shows that the energy band gap decreases with increasing Nd3+ concentration. The photoluminescence spectra (PL) show a broad emission band in the visible region corresponding to the various structural defects and oxygen vacancies in the prepared nanocrystals responsible for the activation of bound magnetic polarons (BMPs). Fitting the experimental magnetization data with the BMP model based on the Langevin function shows that the density of magnetic polarons (1020cm−3) in the doped samples is equal to the typical percolation threshold. The dielectric constant and dielectric loss was observed to increase at lower frequency due to the presence of GBs and oxygen vacancies, and this behavior was explained based on Koop's phenomenological theory. Based on these results, it was demonstrated that the FM response and the dielectric properties in studied samples are strongly associated with GBs and oxygen vacancies.

Refined nuclear magnetic dipole moment of rhenium: Re185 and Re187

The refined values of the magnetic dipole moments of $^{185}$Re and $^{187}$Re nuclei are obtained. For this, we perform a combined relativistic coupled cluster and density functional theory calculation of the shielding constant for the ReO$_4^-$ anion. In this calculation, we explicitly include the effect of the finite nuclear magnetization distribution in the single-particle nuclear model using the Woods-Saxon potential for the valence nucleon. By combining the obtained value of the shielding constant $\sigma=4069(389)$~ppm with the available experimental nuclear magnetic resonance data we obtain the values: $\mu(^{185}{\rm Re})=3.1567(3)(12) \mu_N, \mu(^{187}{\rm Re})=3.1891(3)(12) \mu_N$, where the first uncertainty is the experimental one and the second is due to theory. The refined values of magnetic moments are in disagreement with the tabulated values, $\mu(^{185}{\rm Re})=3.1871(3) \mu_N, \mu(^{187}{\rm Re})=3.2197(3) \mu_N$, which were obtained using the shielding constant value calculated for the atomic cation Re$^{7+}$ rather than the molecular anion. The updated values of the nuclear magnetic moments resolve the disagreement between theoretical predictions of the hyperfine structure of H-like rhenium ions which were based on the tabulated magnetic moment values and available experimental measurements. Using these experimental data we also extract the value of the parameter of nuclear magnetization distribution introduced in [J. Chem. Phys. \textbf{153}, 114114 (2020)], which is required to predict hyperfine structure constants for rhenium compounds.

Windmill-like Ln4 Clusters [Ln = Tb(III) and Dy(III)] Bridged by [α-AsW9O33]9- Unit Showing Zero-Field SMM Behavior: Experimental and Theoretical Investigation.

Herein, two polyoxometalate (POM)-ligated tetranuclear rare-earth metal complexes having the molecular formula [CsxK24-x{Ln4(H2O)8(α-AsW9O33)4}]·yH2O {x = 5, y = 20, and Ln = Tb(III) (1); and x = 6, y = 28, and Ln = Dy(III) (2)} were synthesized by a one-pot reaction with LnCl3·6H2O using di-lacunary [As2W19O67(H2O)]14- precursor and characterized. The structural analysis shows that the building units [α-AsW9O33]9- are bridged by four rare-earth ions, where one [α-AsW9O33]9- bridged two Ln(III) centers asymmetrically by μ2-O and terminal oxygen atoms. The [α-AsW9O33]9- units are orthogonal to each other, resembling as vanes of a windmill. The magnetic studies disclosed the presence of large magnetic anisotropy and slow relaxation of magnetization behavior [Ueff = 15.2 K (1) and 26 K (2)] in the absence of an external magnetic field. Detailed analysis of relaxation dynamics confirmed that the QTM process in 2 (τQTM = 2.50 × 10-4 s) is slower as compared to complex 1 (τQTM = 2.38 × 10-4 s), and the relaxation process mainly follows the shortcut pathways (such as QTM, optical, and acoustic phonon process) rather than the thermally activated Orbach process. Further, the ab initio calculations show high axial ground states with minimum transverse anisotropy and provide a good agreement between calculated and experimental magnetic data for both complexes. It has also been observed that the local symmetry (D4d subgroup) around the metal centers in 1 provides higher axiality and stabilizes mJ = ±6 of Tb(III) more as compared to mJ = ±15/2 of Dy (III) in 2, resulting in higher energy splitting of the ground state in the former complex. The combined experimental and theoretical observations suggest that the high axial nature of the ground state with minimum transverse anisotropy resulting from local ligand field symmetry is responsible for the observed zero-field single-molecule magnet (SMM) behavior in the studied complexes. Notably, complex 1 is the first example of a POM-based terbium complex that shows SMM behavior in the absence of an external field.

Molecular Magnetic Materials Based on {CoIII (Tp*)(CN)3 }- Cyanidometallate: Combined Magnetic, Structural and 59 Co NMR Study.

The cyanidocobaltate of formula fac‐PPh4[CoIII(Me2Tp)(CN)3] ⋅ CH3CN (1) has been used as a metalloligand to prepare polynuclear magnetic complexes (Me2Tp=hydrotris(3,5‐dimethylpyrazol‐1‐yl)borate). The association of 1 with in situ prepared [FeII(bik)2(MeCN)2](OTf)2 (bik=bis(1‐methylimidazol‐2‐yl)ketone) leads to a molecular square of formula {[CoIII{(Me2Tp)}(CN)3]2[FeII(bik)2]2}(OTf)2 ⋅ 4MeCN ⋅ 2H2O (2), whereas the self‐assembly of 1 with preformed cluster [CoII 2(OH2)(piv)4(Hpiv)4] in MeCN leads to the two‐dimensional network of formula {[CoII 2(piv)3]2[CoIII(Me2Tp)(CN)3]2 ⋅ 2CH3CN}∞ (3). These compounds were structurally characterized via single crystal X‐ray analysis and their spectroscopic (FTIR, UV‐Vis and 59Co NMR) properties and magnetic behaviours were also investigated. Bulk magnetic susceptibility measurements reveal that 1 is diamagnetic and 3 is paramagnetic throughout the explored temperature range, whereas 2 exhibits sharp spin transition centered at ca. 292 K. Compound 2 also exhibits photomagnetic effects at low temperature, selective light irradiations allowing to promote reversibly and repeatedly low‐spin⇔high‐spin conversion. Besides, the diamagnetic nature of the Co(III) building block allows us studying these compounds by means of 59Co NMR spectroscopy. Herein, a 59Co chemical shift has been used as a magnetic probe to corroborate experimental magnetic data obtained from bulk magnetic susceptibility measurements. An influence of the magnetic state of the neighbouring atoms is observed on the 59Co NMR signals. Moreover, for the very first time, 59Co NMR technique has been successfully introduced to investigate molecular materials with distinct magnetic properties.

Diluting a triangular-lattice spin liquid: Synthesis and characterization of NaYb1−xLuxS2 single crystals

Yb-based magnets, with a perfect triangular lattice of pseudospin-$\frac{1}{2}\phantom{\rule{4pt}{0ex}}{\mathrm{Yb}}^{3+}$ ions, have emerged as candidates for realizing a quantum spin-liquid state, with ${\mathrm{NaYbS}}_{2}$ being a prominent example. Here, we present the solid-solution series ${\mathrm{NaYb}}_{1\ensuremath{-}x}{\mathrm{Lu}}_{x}{\mathrm{S}}_{2}$ with well-defined single crystals over the entire substitution range $0\ensuremath{\le}x\ensuremath{\le}1$. Chemical and structural analysis indicate a statistically homogeneous replacement of ${\mathrm{Yb}}^{3+}$ by ${\mathrm{Lu}}^{3+}$ ions. We magnetically characterize the relatively small single crystals using electron spin resonance (ESR). Below $30\phantom{\rule{0.16em}{0ex}}\mathrm{K}$, the ESR intensity can be well described by a Curie-Weiss function for all $x$, with a decreasing Weiss temperature with increasing Lu content. This reduction of the average magnetic interaction upon Lu substitution is also supported by magnetization measurements. Importantly, no signs of magnetic or spin-glass order are detected down to $2\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ for any $x$. For $x&gt;0.5$, the ESR linewidth strongly increases, indicating the breakup of the magnetic system into disconnected clusters, as expected from percolation physics. The experimental magnetization data are found to be in good agreement for all $x$ with results of classical Monte Carlo simulations for a triangular-lattice Heisenberg model, amended with a small second-neighbor interaction. Taken together, our results establish ${\mathrm{NaYb}}_{1\ensuremath{-}x}{\mathrm{Lu}}_{x}{\mathrm{S}}_{2}$ as a family of diluted triangular-lattice spin liquids.