Magnetic Susceptibility Measurements Research Articles

Valence tautomeric interconversion of bis-dioxolene cobalt complex with imino-pyridine functionalized by TEMPO moiety in solid solutions with isostructural nickel analogue: phase transitions and monocrystal destruction.

Valence tautomeric complexes (VT) are promising systems for creating molecular devices. From this viewpoint, valence tautomeric complexes with a hysteresis loop on the magnetic curve are of special interest as potential memory elements. The hysteresis loop is a consequence of retarded structural rearrangements which investigation is an actual problem. Recently, we have described a new VT transition taking place in a bis-dioxolene cobalt complex with imino-pyridine having a TEMPO substituent (A. A. Zolotukhin, et al., Inorg. Chem., 2017, 56, 14751-14754). Valence tautomeric transformation occurs with a hysteresis loop and is accompanied by a phase transition. The phase transition taking place during cooling is accompanied by crystal destruction. This fact makes it impossible to monitor the structural changes responsible for the hysteresis loop. The current research attempts to resolve this problem. A nickel compound of the same composition (TEMPO-imino-pyridine)Ni(3,6-DBSQ)2 was synthesized and characterized. It was established to be isostructural with the cobalt complex. It was used as an inert matrix for the dilution of the VT cobalt complex. The number of solid solutions with Co/Ni ratios of 1 : 1, 1 : 2, 1 : 4, and 1 : 8 was obtained. Variable temperature magnetic susceptibility measurements show that VT transformation with a hysteresis loop takes place in all solid solutions. The hysteresis loop is shifted to low temperatures primarily due to the shifting of its low-temperature boundary with dilution. The hysteresis width does not change significantly with dilution. DSC detected that transformations are accompanied by phase transitions at different temperatures at cooling and heating. The phase transition at the first cooling occurs at slightly lower temperatures compared with subsequent cycles. These temperatures correspond to the transition temperatures detected from the magnetic curves. The phase transition during the first cooling is accompanied by crystal destruction. Physical destruction takes place in the crystals of all solid solutions. X-ray diffraction powder patterns confirm that phase transition is accompanied by considerable reorganization of the crystal structure typical for the first order transitions. The unit cell volume of solid solutions is larger than that of pure complexes. Especially calculated crystal invariom indicated that the "lattice energy" in a solid solution is the lowest compared with that in "pure" nickel and cobalt complexes.

Contribution to the physicochemical characterisation of soils in the Beni Boufrah watershed (Central Rif, Morocco)

As part of the study of soil water erosion in the Beni Boufrah watershed, which forms part of the northern slopes of the Central Rif, generally dipping towards the Mediterranean Sea, we carried out soil analyses to determine certain physicochemical characteristics of the soil. These analyses, which consisted of measuring pH, estimating residual moisture content, organic matter and carbonates, and measuring magnetic susceptibility in the horizons of eight profiles sampled from different soils in the Beni Boufrah watershed, are of great interest in understanding the behaviour of these soils with regard to water erosion. The results obtained show that the soils in this catchment area are alkaline, and that their residual moisture and organic matter content are remarkably low, especially in the surface horizons. The carbonate content is only significant in soils resulting from the alteration of parent rocks belonging to the Bokkoya limestone ridge. Magnetic susceptibility measurements show that the soils studied are disturbed and reworked.

Spin canting and slow magnetic relaxation in mononuclear cobalt(II) sulfadiazine ternary complexes.

Monomeric [Co(SDZ)2phen] (1) and [Co(SDZ)(bq)Cl] (2) complexes (SDZ = sulfadiazine, phen = 1,10-phenanthroline, and bq = 2,2'-biquinoline) have been synthesized and characterized. X-ray diffraction studies indicate that SDZ acts as a bidentate ligand coordinating through the sulfonamide and the pyrimidine N atoms in both compounds. In complex 1, the coordination sphere consists of two SDZ ligands and a bis-chelating phen ligand, giving rise to a CoN6 coordination sphere. On the other hand, 2 has a CoN4Cl core, with two N-atoms from SDZ and two from the bq ligand. Both compounds have been studied by dc and ac magnetometry and shown to display slow magnetic relaxation under an optimum external dc field (1 kOe) at low temperatures. Moreover, compound 2 displays long range magnetic ordering provided by spin-canted antiferromagnetism, which has been characterized by further field-dependent magnetic susceptibility measurements, FC/ZFC curves, hysteresis loops and frequency-independent ac curves. The signs of the calculated D parameters, positive in 1 and negative in 2, have been rationalized according to the two lowest-lying transitions in the orbital energy diagrams derived from ab initio ligand field theory (AILFT). In a subsequent attempt to reveal the possible hidden zero-field SMM behaviour, Ni(II)-based 3 and Co(II)-doped Ni(II)-based (with a Ni : Co ratio of 0.9 : 0.1) heterometallic compound 2Ni were synthesized.

Geometry and electronic structure of Yb(III)[CH(SiMe3)2]3 from EPR and solid-state NMR augmented by computations.

Characterization of paramagnetic compounds, in particular regarding the detailed conformation and electronic structure, remains a challenge, and - still today it often relies solely on the use of X-ray crystallography, thus limiting the access to electronic structure information. This is particularly true for lanthanide elements that are often associated with peculiar structural and electronic features in relation to their partially filled f-shell. Here, we develop a methodology based on the combined use of state-of-the-art magnetic resonance spectroscopies (EPR and solid-state NMR) and computational approaches as well as magnetic susceptibility measurements to determine the electronic structure and geometry of a paramagnetic Yb(III) alkyl complex, Yb(III)[CH(SiMe3)2]3, a prototypical example, which contains notable structural features according to X-ray crystallography. Each of these techniques revealed specific information about the geometry and electronic structure of the complex. Taken together, both EPR and NMR, augmented by quantum chemical calculations, provide a detailed and complementary understanding of such paramagnetic compounds. In particular, the EPR and NMR signatures point to the presence of three-centre-two-electron Yb-γ-Me-β-Si secondary metal-ligand interactions in this otherwise tri-coordinate metal complex, similarly to its diamagnetic Lu analogues. The electronic structure of Yb(III) can be described as a single 4f13 configuration, while an unusually large crystal-field splitting results in a thermally isolated ground Kramers doublet. Furthermore, the computational data indicate that the Yb-carbon bond contains some π-character, reminiscent of the so-called α-H agostic interaction.

Insight into ferromagnetic interactions in CuII-LnIII dimers with a compartmental ligand.

In the last two decades, efforts have been devoted to obtaining insight into the magnetic interactions between CuII and LnIII utilizing experimental and theoretical means. Experimentally, it has been observed that the exchange coupling (J) in CuII-LnIII systems is often found to be ferromagnetic for ≥4f7 metal ions. However, exchange interactions at sub-Kelvin temperatures between CuII and the anisotropic/isotropic LnIII ions are not often explored. In this report, we have synthesized a series of heterobimetallic [CuLn(HL)(μ-piv)(piv)2] complexes (LnIII = Gd (1), Tb (2), Dy (3) and Er (4)) from a new compartmental Schiff base ligand, N,N'-bis(3-methoxy-5-methylsalicylidene)-1,3-diamino-2-propanol (H3L). X-ray crystallographic analysis reveals that all four complexes are isostructural and isomorphous. Magnetic susceptibility measurements reveal a ferromagnetic coupling between the CuII ion and its respective LnIII ion for all the complexes, as often observed. Moreover, μ-SQUID studies, at sub-Kelvin temperatures, show S-shaped hysteresis loops indicating the presence of antiferromagnetic coupling in complexes 1-3. The antiferromagnetic interaction is explained by considering the shortest Cu⋯Cu distance in the crystal structure. The nearly closed loops for 1-3 highlight their fast relaxation characteristics, while the opened loops for 4 might arise from intermolecular ordering. CASSCF calculations allow the quantitative assessment of the interactions, which are further supported by BS-DFT calculations.

Tetranuclear NiII-Mannich base complex with oxygenase, water splitting and ferromagnetic and antiferromagnetic coupling properties.

A new Mannich base (2-(4-(2-hydroxy-3-methoxy-5-methylbenzyl)-piperazin-1-yl)methyl)-6-methoxy-4-ethylphenol (H2L) and its tetranuclear NiII complex [Ni4L2(μ1,1-Cl)2(H2O)4]Cl2 (compound 1) are characterised using single-crystal X-ray diffraction measurements. Compound 1 contains four different NiII centres in a rhombus-like structure. Two Ni atoms (Ni1 and Ni2) have a NiN2O4 coordination sphere, while the other two (Ni3 and Ni4) have a NiO4Cl2 coordination environment and Ni-Cl-Ni bridges connect them. Ni1 and Ni2 are linked to Ni3 and Ni4 by phenoxide bridges. Variable temperature magnetic susceptibility measurements of 1 indicate the presence of alternating antiferromagnetic coupling (J1 = -6.6(1) cm-1) through the phenoxide bridge along the sides of the rhombus and ferromagnetic coupling (J2 = 8.4(1) cm-1) through the double Cl bridge along the short diagonal of the rhombus with a zero-field splitting of |D| = 2.7(1) cm-1. Compound 1 shows oxidase (catecholase-like and phenoxazinone synthase-like) activity. The oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) gives 3,5-di-tert-butylquinone (3,5-DTBQ) and H2O2 and the oxidation of o-aminophenol (OAP) produces 2-aminophenoxazin-3-one (APX) and H2O with turnover numbers of 28.32 and 17.52 h-1, respectively, under aerobic conditions. A mechanism for the oxidase activity catalysed by compound 1 is proposed in line with ESI-mass spectrometry, EPR spectroscopy, and electrochemical data. The reaction involves the cleavage of the tetranuclear Ni4-core to form a mononuclear NiII complex in the presence of the substrate (3,5-DTBC/OAP). This NiII complex is reduced to NiI with the concomitant oxidation of the substrate (3,5-DTBQ/APX). Formation of a radical intermediate is confirmed using EPR. In the catecholase-like activity, O2 is reduced to H2O2 while in the phenoxazinone synthase-like activity O2 produces H2O. Compound 1 participated in oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in a strongly basic medium with an onset potential of 418 mV and a Tafel slope of 121 mV dec-1 for OER and an onset potential of 477 mV and Tafel slope of 146 mV dec-1 for HER.

The effect of the gelation temperature on the structural, magnetic and magnetocaloric properties of perovskite nanoparticles manufactured using the sol-gel method.

This study presents a comprehensive investigation of the structural and magnetic properties of La0.8Sr0.2Mn0.8Co0.2O3 (LS1, LS2 and LS3) compounds synthesized via the sol-gel method at different gelation temperatures through X-ray diffraction and different magnetic measurement techniques. The Rietveld refinement demonstrated that all samples exhibit a rhombohedral perovskite structure with the R3̄C space group. Their magnetic behavior, characterized through magnetization measurements, hysteresis loops, and Arrot plots, demonstrates a ferromagnetic-paramagnetic transition with notable soft ferromagnetic characteristics. The samples also demonstrate second-order magnetic transitions, short-range magnetic order and the presence of both ferromagnetic and antiferromagnetic contributions. AC magnetic susceptibility measurements, allowing the investigation of the magnetic dynamics of the samples, shows that the Vogel-Fulcher and the Conventional Critical Slowing Down models are the most appropriate for describing the dynamic behavior, confirming the spin-glass nature of the compounds and the presence of medium to strong interaction between magnetic nanoparticles. The influence of gelation temperature in the magnetocaloric effect of the compounds was proven and LS1, synthesized at the lowest gelation temperature (70 °C), exhibits the higher magnetic entropy change (|ΔSmax| = 3.25 J kg-1 K-1 and RCP = 209.83 J kg-1 at 5 T). For a better evaluation of the magnetocaloric efficiency, the temperature average entropy change (TEC) parameter was calculated for all three samples and LS1 showed the highest value (TEC (LS1) ∼3.2 J kg-1 K-1 for ΔTH-C = 10 K and ΔH = 5 T).

Impact of flexible hexyl chain ordering in a mononuclear spin crossover iron(III) complex.

A novel FeIII complex [Fe(Hex-tnal)2]BPh4 (1) with a tridentate N2O ligand having an n-hexyl chain, Hex-Htnal (=1-((((1-hexyl-1H-1,2,3-triazol-4-yl)methyl)imino)methyl)naphthalen-2-ol), is reported. Temperature-dependent magnetic susceptibility measurements revealed that 1 exhibits a two-step spin crossover (SCO) transition in the 400-10 K temperature range, including an unusual gradual χMT change above RT (300-345 K) and a hysteretic χMT jump in a narrow temperature range of 345-357 K. These behaviors were also characterized by differential scanning calorimetry. Variable-temperature single-crystal X-ray diffraction studies revealed that the order-disorder transition and conformational change of the hexyl chains and the symmetry change associated with the re-entrant structural phase transition, namely triclinic P1̄ (100-275 K) ↔ monoclinic C2/c (296-340 K) ↔ triclinic P1̄ (360 K), are coupled to variations in intermolecular interactions and the N4O2 coordination environment, resulting in the occurrence of the unusual two-step SCO transition of 1. This study demonstrates that the flexible motion of alkyl substituents in the supramolecular lattice influences the occurrence of anomalous magnetic switching properties.

Synthesis, characterization, electron paramagnetic property and catalytic amidation of binuclear ruthenium(III) complexes

A series of new binuclear ruthenium(III) complexes [ Ru2Cl4(EPh3)4(L)] (E = P or As) were successfully synthesized from 1:2 mol ratio of bi-nucleating ligand precursors (L1H2-L3H2) and [RuCl3(EPh3)3] in benzene for 6 h. The complexes were characterized by elemental analysis, FT-IR, UV–vis, magnetic susceptibility measurements and EPR spectroscopy methods. Rhombic distortion (gx ≠ gy ≠ gz) around the ruthenium ion was confirmed by EPR spectra in liquid nitrogen temperature. Catalytic activity of the facile one pot amidation reaction has been developed. The complex [Ru2Cl4(AsPh3)4(L1)](4) was found to possess excellent conversion up to 100 % of amide in toluene with the presence of hydroxylamine hydrochloride and NaHCO3 at 110 °C in 2 h. The effect of time, temperature, solvents and different catalytic loading experiments was also investigated.

Synthesis and Structural Views on New Azo Ligand and Its Metal Complexes with Some of their Application

In this work, we presented a study of the structural formula for a new series of complexes with Ag(I), Cu(II), Zn(II), and Cd(II) derived from the guanine azo dye ligand 2-amino-8-((3-hydroxyphenyl)diazinyl)-1,7-dihydro-6H-purin-6-one (HAG), which is investigated using various physicochemical analyses, spectroscopic techniques (FT-IR, U.V-VIS, and 1H NMR), thermogravimetric analysis (TGA). In addition, elemental analyses, magnetic susceptibility, and molar conductance measurements were all stabilized. As well as the mole ratio, stability constant, and Gibbs free energy were studied for all complexes, where they showed high stability and spontaneous synthesis. The Cu(II) complex was suggested to have octahedral stereochemistry, while the Ag(I), Zn(II), and Cd(II) complexes were suggested to have tetrahedral stereochemistry. The ligand has been demonstrated to be a useful acid-base indicator, and it has been shown that the ligand (HAG) and its complexes exhibit high photostability and have various colors that can be used to dye wool materials.

Oxidation of phosphine donors to phosphinimines via a putative Fe-imido intermediate

The formation of FeII phosphinimine complexes by treatment of an S = 1 (PNNP)FeII complex with MesN3 (Mes = 2,4,6-trimethylphenyl) is reported. The resulting compounds have been characterized structurally and spectroscopically. Zero-field 57Fe Mössbauer spectroscopy and magnetic susceptibility measurements suggest a spin-state change occurs once both phosphines have been converted to phosphinmines, commensurate with the weaker field nature of phosphinimine ligands compared to phosphines. We propose that phosphine oxidation proceeds through nitrene transfer to Fe to afford a formally FeIV-imido intermediate that is more accurately predicted to have FeIII-imidyl radical character. Although no such intermediate could be isolated due to its instability and rapid phosphine oxidation, we support this mechanistic proposal with stoichiometric experiments and in silico analyses at the ωB97X-D3/def2-SVP level of theory. Our computational analyses confirm that the driving force for this transformation is very favorable.

Synthesis and characterization of Co (II), Ni (II) and Cu (II) complexes with unsymmetrical tetradentate Schiff base ligand

A novel series of cobalt (II), nickel (II) and copper (II) complexes of unsymmetrical Schiff base ligand 1-(2-hydroxynaphthalideneimino)-2-(5 methoxysalicylidene imino)-4 chlorobenzene-1,2-diamine was synthesised by condensation reaction of 1:1:1 molar ratio of 2-hydroxynaphthalene-1-carbaldehyde, 4-chlorobenzene -1,2-diamine and 5-methoxysalicyidehyde in alcoholic medium. The synthesised ligand and its metal complexes were characterised by elemental analysis, molar conductance measurements, magnetic susceptibility measurements, UV-Vis and infrared spectral data. The molar conductance of synthesised metal complexes in DMSO solution indicates their non-electrolytic nature. The analytical data show the general formula for the complexes to be [M(L)2] where L = Schiff base ligand and M = Co (II), Ni (II) and Cu (II). The spectral data and magnetic moment suggested that Schiff base behaves as a tetradentate ligand, coordinating through azomethine nitrogen and phenolic oxygen atoms to the metal ion. Magnetic susceptibility measurements, UV-Vis and infrared spectral data geometry of metal complexes were proposed to be square planar.

Synthesis, Characterization and Antibacterial Activity of Sn(II) and Sn(IV) Ions Complexes Containing N-Alkyl-N-Phenyl Dithiocarbamate Ligands

In the current study, ligands S2 donor atoms, sodium N-methyl-N-phenyldithiocarbamate [L1], and sodium N-ethyl-N-phenyldithiocarbamate [L2] are prepared from carbon disulfide with N-methyl aniline and N-ethyl aniline, respectively. Sn(II) and Sn(IV) ions complexes containing N-alkyl-N-Phenyl dithiocarbamateare prepared and characterized by CHNS elemental analysis, infrared spectroscopy (FT-IR), 1HNMR-spectroscopy, mass spectroscopy, UV-visible spectroscopy, magnetic susceptibility and conductivity measurements. The analytical and spectral data show that the stoichiometry for all complexes is 1 : 2 metal to ligand. The spectral data confirm good coordination of dithiocarbamate ligand with the metal through sulfur atoms of dithiocarbamate moiety. Molar conductivity of complexes are measured using DMF as a solvent and indicated that the complexes of Sn(II) are non-ionic whereas Sn(IV) complexes are ionic. The ligands L1 and L2 and their complexes are examined against Staphylococcus aureus bacteria and Escherichia coli bacteria.

The HfFe2Si2 type silicides ScT 2Si2 (T = Ru, Rh, Os) – structure and solid-state 29Si/45Sc NMR spectroscopy

Abstract The silicides ScT 2Si2 (T = Ru, Rh, Os) were synthesized by arc-melting of the elements and subsequent annealing in sealed silica ampoules. They crystallize with the rarely observed HfFe2Si2 type structure, space group Pbcm. The structures of ScRu2Si2 (a = 761.64(4), b = 730.70(6), c = 521.07(6) pm, wR = 0.0314, 633 F 2 values, 31 variables) and ScOs2Si2 (a = 771.10(8), b = 736.68(7), c = 521.88(5) pm, wR = 0.0479, 623 F 2 values, 31 variables) were refined from single crystal X-ray diffractometer data. The refinements showed small degrees of Ru/Si respectively Os/Si mixing on one 4c site, leading to the refined compositions ScRu1.96(1)Si2.04(1) and ScOs1.91(1)Si2.09(1). The monomeric building units in both structures are two slightly distorted, crystallographically independent RuSi5 respectively OsSi5 square pyramids, which are condensed via common edges. The resulting densely packed [Ru2Si2] and [Os2Si2] networks leave voids for the scandium atoms with coordination number 18: Sc@Si8Ru8Sc2 and Sc@Si8Os8Sc2. Temperature dependent magnetic susceptibility measurements of ScRu2Si2 and ScOs2Si2 indicate Pauli paramagnetism. Solid-state 29Si and 45Sc static and MAS NMR spectroscopy reveal significant Knight shifts and a strong influence of the T/Si mixing on the experimental NMR line shapes. A larger overall 29Si magnetic shift for ScRu2Si2 compared to ScOs2Si2, although with a negative sign for one of the 29Si resonances, suggests stronger paramagnetic effects for ScRu2Si2, in agreement with the magnetic susceptibility measurements.

Copper(I) complexes of 1,2-bis(diphenylphosphino)benzene as efficient catalysts for alkyne hydroamination and azide-alkyne cycloaddition

This paper reports the synthesis of a small group of three copper(I) complexes using 1,2-bis(diphenylphosphino)benzene, abbreviated as dppbz, and their utilization as catalyst for CN bond formation reactions. Reaction of dppbz has been carried out with three different copper(I) sources. While reaction with [Cu(CH3CN)4]ClO4 affords [CuI(dppbz)2]ClO4 (complex 1), that with CuI and CuSCN affords di-copper complexes [{CuI(dppbz)I}2] and [{CuI(dppbz)(SCN)}2] (complexes 2 and 3) respectively. Bulk characterization on the complexes has been done by elemental (C, H, N) analysis, magnetic susceptibility measurement, and spectroscopic (IR, NMR and UV–vis) methods. Crystal structures of all three complexes have been determined. In [CuI(dppbz)2]ClO4, copper(I) is having a highly distorted tetrahedral CuP4 core. In [{CuI(dppbz)I}2] and [{CuI(dppbz)(SCN)}2], the tetrahedral CuP2I2 and CuP2SN cores are relatively less distorted. These copper complexes have been found to serve as efficient catalyst precursors for two types of CN bond formation reactions, viz. hydroamination and click reaction. Hydroamination of aryl alkynes with aryl amines has afforded selectively imine products of a single type (Markownikov product) in good yields under relatively mild condition. However, similar hydroamination with benzyl amines or alkyl amines has afforded selectively anti-Markownikov imine products. Click reaction between aryl alkynes and aryl azides yielding the cycloaddition products has also been brought about successfully with remarkable catalytic efficiency.

Measuring magnetic susceptibility of particulate matter collected on filters

The magnetic susceptibility (κ) of particulate matter (PM) is a useful tool in estimation concentration of iron-rich particles and provides useful information on the emission sources and pathways of spread of PM in the atmosphere. However, there is currently no established protocol for measuring the magnetic susceptibility of PM collected on filters used in standard monitoring of PM concentration. This paper presents a step-by-step process for collecting PM on filters in automatic samplers and measuring their κ. The procedure outlines requirements for data quality, measurement uncertainty, exposure time and conditions, and the amount of material collected on the filters. The study analyzed a 2-year dataset of magnetic susceptibility measurements by MFK-1 kappabridge (Agico, Czech Republic) for PM10 and PM2.5 collected at two locations, Warsaw and Cracow, in Poland using low-volume PM samplers. By strictly following the procedure for conditioning filters, measuring magnetic susceptibility and mass of PM, the study found that it is possible to obtain repeatable data with good measurement accuracy and acceptable errors. This makes magnetic susceptibility an additional reliable parameter for tracking of emission sources of iron-rich particles. Successful implementation of this magnetic method as a standard procedure for monitoring PM in addition to the PM mass collected on filters could be used to analyze sources of emission of Fe-particles and their contribution to the PM mass, especially in urban and industrial environments.

High-Pressure Synthesis, Crystal Structure, and Physical Properties of a Spinel Compound Co0.7Al2S4.

In this paper, we report on the discovery of a spinel compound, Co0.7Al2S4, which was synthesized at high-pressure. The systematic characterizations were carried out by structural, magnetic, and heat capacity measurements. The compound crystallizes into a cubic structure with the space group Fd3̅m (no. 227) and the lattice constant a = 9.9580(1) Å. Magnetic susceptibility measurements suggest that Co0.7Al2S4 exhibits a spin glass ground state, freezing at Tf ∼ 7.2 K with a Weiss temperature Tθ ∼ -115.9 K, which is verified by ac magnetic susceptibility and heat capacity measurements. The frustration parameter f for Co0.7Al2S4 is calculated to be about 16.6, based on the formula f = | Tθ/Tf |, indicating that Co0.7Al2S4 is a high-frustration magnet. Specific heat data displays a T2 dependence below the freezing temperature, which is different from the linear dependence observed in a common spin glass system. Compared with the similar compound CoAl2O4, it is suggested that the vacancies in the Co sites should be responsible for the occurrence of the spin glass behavior of Co0.7Al2S4.

Magnetic and magneto-optical properties of manganese-containing antimony phosphate glasses – An alternative to Faraday rotators

Glasses in system 100-x(70SbPO4–10ZnO–20PbO) xMnO, with x = 0, 10, 20 and 30 mol %, where prepared by the conventional melting-quenching method. The glasses were cut, polished and characterized by XRD, DSC, Raman, FTIR, UV–Vis and luminescence and magnetic and magneto-optical aiming application ultimate as in magneto-optical devices. These samples containing manganese exhibit magnetic response to neodymium magnets at room temperature. In addition, they feature thermal stability above 100 °C, wide transparency in the visible and near infrared region. The optical absorption spectra of the glass revealed the presence of characteristic absorption bands of Mn2+ at 410 nm attributed to 6A1(S) → 4A1, 4E (4G) transition and possible oxidation at around 550 nm assigned to 5B1g → 5B2g transition of the Mn3+ ions. Refractive indices higher than 1.8 and characteristic emission bands around 680–720 nm, assigned to 4T1(G)→6A1(S) transition, were also observed. Magnetic susceptibility measurements revealed the paramagnetic character of the Mn-containing glasses, with antiparallel spin alignment. Finally, a linear growth trend was observed for the Verdet constant along with the Mn2+ concentration and the highest value measured, for sample containing 30 mol% of MnO, was −55.1 ± 3.2 rad T−1 m−1 at 632.8 nm. This value is close to those of some families of glasses containing rare earths, being an alternative of new low-cost magneto-optical vitreous materials.

Influence of the ancillary ligand on the crystalline structures and magnetic properties of mesaconato‐bridged Mn coordination polymers

Abstract{[Mn(mes)(dmb)(H2O)] ⋅ H2O}n (1) and [Mn(mes)(bpy)]n (2); (mes=mesaconato; dmb=5,5’‐dimethyl‐2,2’‐bipyridine; bpy=2,2’‐bipyridine), were obtained by self‐assembly solution reaction at ambient conditions, and structurally characterized by single crystal X‐ray diffraction. 1 crystallizes in an orthorhombic system with a Pbca space group and forms a one‐dimensional (1D) coordination polymer; the six‐coordinated Mn(II) centers display a distorted‐trigonal prismatic configuration. 2 crystallizes in an orthorhombic system with a P21212 space group yielding a two‐dimensional (2D) coordination array, their metal centers having a distorted octahedral geometry. Magnetic susceptibility measurements reveal that 1 is paramagnetic, while 2 shows weak antiferromagnetic coupling.

The Kondo Effect in CexLaLuScY (x = 0.05-1.0) High-Entropy Alloys.

In the search for electronic phenomena in high-entropy alloys (HEAs) that go beyond the independent-electron description, we have synthesized a series of hexagonal rare earth (RE)-based HEAs: CexLaLuScY (x = 0.05-1.0). The measurements of electrical resistivity, magnetic susceptibility and specific heat have shown that the CexLaLuScY HEAs exhibit the Kondo effect, which is of a single impurity type in the entire range of employed Ce concentrations despite the alloys being classified as dense (concentrated) Kondo systems. A comparison to other known dense Kondo systems has revealed that the Kondo effect in the CexLaLuScY HEAs behaves quite differently from the chemically ordered Kondo lattices but quite similar to the RE-containing magnetic metallic glasses and randomly chemically disordered Kondo lattices of the chemical formula RE1xRE21-xM (with RE1 being magnetic and RE2 being nonmagnetic). The main reason for the similarity between HEAs and the metallic glasses and chemically disordered Kondo lattices appears to be the absence of a periodic 4f sublattice in these systems, which prevents the formation of a coherent state between the 4f-scattering sites in the T→ 0 limit. The crystal-glass duality of HEAs does not bring conceptually new features to the Kondo effect that would not be already present in other disordered dense Kondo systems. This study broadens the classification of HEAs to correlated electron systems.