Current Magnetic Susceptibility Research Articles

Alcohol-bridged dinuclear dysprosium single-molecule magnets

Herein we showcase triple-bridged symmetric dinuclear dysprosium complexes with the core structure of general chemical formula Dy2(L1)2(L2)2(R-OH) (R = Me, 1; Et, 2; iPr, 3; pHCH2, 4) involving bridging alcohol molecules. L1 and L2 represent the deprotonated form of oxazole 4‑tert‑butyl‑2-(7-methoxybenzo[d]oxazol-2-yl)phenol and Schiff-base (E)-2,4-di‑tert‑butyl‑6-((3,5-di‑tert‑butyl‑2-hydroxybenzylidene)amino)phenol, respectively. Single-crystal X-ray structural characterization revealed an unprecedented long Dy-O bond length for the benzyl alcohol analogue. The corresponding long Dy-O bond lengths in 1–4 are 2.7825, 2.6651, 2.6021 and 2.9955 Å, respectively. Alternating current magnetic susceptibility measurements at zero dc field revealed that all four complexes display clear frequency dependence signal peaks, indicating single-molecule magnet behavior. The spin reversal energy barrier heights for 1, 2 and 4 are 31.1, 27.6 and 17.4 K. The dynamic magnetic behavior is influenced by the different Dy-O bond lengths derived from the bridging alcohol molecules. Theoretical calculations were employed to establish magneto-structural correlations in 1–4. Magneto-structural correlations with respect to the alcohol molecule participating in triple-bridged symmetric dinuclear dysprosium complexes is established with the help of quantum-chemical calculations.

Field-Induced Slow Magnetization Relaxation of a Tetrahedral S=2 FeIIS4-Containing Complex.

In the work described herein, the spin relaxation properties of the mononuclear tetrahedral S = 2 [Fe{(SPiPr2)2N}2] complex (1) were studied by employing static and dynamic magnetic measurements al liquid helium temperatures. In the absence of an external direct current (DC) magnetic field, 1 exhibits fast magnetization relaxation. However, in the presence of external magnetic fields of a few kOe, slow relaxation is induced as monitored by alternating current (AC) magnetic susceptibility measurements up to 10 kHz, in the temperature range 2-5 K. Analysis of the temperature dependence of the corresponding relaxation time reveals contributions by Quantum Tunnelling of Magnetization, and the Direct and Orbach processes in the magnetization relaxation mechanism of 1. The energy barrier, Ueff, of the Orbach process, as determined by this analysis, is compared with that related to the zero field splitting parameters of 1 which were previously determined by high- frequency and -field electron paramagnetic resonance and Mössbauer spectroscopies.

Synthesis and Properties of La14TME6CuS24O4, Exhibiting Multivalent Spin Chains (TME = Cr, Fe).

Two homologues in a series of quinary oxysulfides, La14TME6CuS24O4 (TME = Cr or Fe), have been synthesized by solid-state synthesis in sealed ampules, and their structures are homologue to assume a novel crystal structure. X-ray diffraction analyses of single crystal and powder samples give a monoclinic lattice, described in the C2/m (No. 12) space group, with lattice parameters a = 15.3853(5) Å, b = 13.9729(5) Å, c = 10.5074(4) Å, and β = 116.227(3)° for the Cr analogue and a = 15.4303(2) Å, b = 14.0033(2) Å, c = 10.4909(2) Å, and β = 116.261(2)° for Fe. The crystal structure contains one-dimensional (1D) chains consisting of interconnected transition metal element (TME) trimers, which are further arranged into two-dimensional (2D) layers. These spin-chain planes are interspaced with 1D chains of lanthanum-oxygen coordinations and an apparent disordered occupation of copper sites. Alternating current (AC) and direct current (DC) magnetic susceptibility measurements show that the Cr and Fe analogues exhibit what is best described as spin-domain formation. Density functional theory (DFT) calculations suggest the formal oxidation state of the species is best represented in the form La14TME52+TME3+Cu+S24O4.

A Dinuclear Copper(II) Complex Electrochemically Obtained via the Endogenous Hydroxylation of a Carbamate Schiff Base Ligand: Synthesis, Structure and Catalase Activity.

In the present work, we report a neutral dinuclear copper(II) complex, [Cu2(L1)(OH)], derived from a new [N,O] donor Schiff base ligand L1 that was formed after the endogenous hydroxylation of an initial carbamate Schiff base H2L coordinated with copper ions in an electrochemical cell. The copper(II) complex has been fully characterized using different techniques, including X-ray diffraction. Direct current (DC) magnetic susceptibility measurements were also performed at variable temperatures, showing evidence of antiferromagnetic behavior. Its catalase-like activity was also tested, demonstrating that this activity is affected by temperature.

Mixed‐Valence Manganese Carboxylate Clusters, {MnIII6MnII4}, {MnIII7MnII5Na}, and {MnIII7MnII5}, Derived from the Combined Use of Di‐2‐pyridyl Ketone with Selected Aliphatic Diols

AbstractThree new polynuclear clusters with the formulae [Mn10O4(OH)(OMe){(py)2C(O)2}2{(py)2C(OMe)(O)}4(MeCO2)6](ClO4)2 (1), Na[Mn12O2(OH)3(OMe){(py)2C(O)2}6{(py)2C(OH)(O)}2(MeCO2)2(H2O)10](ClO4)8 (2) and [Mn12O4(OH)2{(py)2C(O)2}6{(py)2C(OMe)(O)}(MeCO2)3(NO3)3(H2O)(DMF)2](NO3)2 (3) were prepared from the combination of di‐2‐pyridyl ketone, (py)2CO, with the aliphatic diols (1,3‐propanediol (pdH2) or 1,4‐butanediol (1,4‐bdH2)) in Mn carboxylate chemistry. The reported compounds do not include the aliphatic diols employed in this reaction scheme; however, their use is essential for the formation of 1–3. The crystal structures of 1–3 are based on multilayer cores which, to our knowledge, are reported for the first time in Mn cluster chemistry. Direct current (dc) magnetic susceptibility studies showed the presence of dominant antiferromagnetic exchange interactions within 1–3. Alternating current (ac) magnetic susceptibility studies revealed the presence of out‐of‐phase signals below 3.0 K for 2 and 3 indicating the slow relaxation of the magnetization vector, characteristic of single‐molecule magnets; the Ueff value of 2 was found to be 23 K and the preexponential factor τ0 ~7.6×10−9 s.

Magnetic collective state formation upon tuning the interparticle interactions in ensembles of ultrafine ferrihydrite nanoparticles

The results of a study of the dynamic (alternating current magnetic susceptibility) and static magnetic properties, as well as 57Fe Mössbauer spectrometry and ferromagnetic resonance of two-line ferrihydrite nanoparticle systems with varying intensities of magnetic interparticle interactions are reported. The strength of the magnetic interparticle interactions has been tuned by coating (with various degrees of coating) the ferrihydrite particles (2–4 nm in size and an average size ∼2.7 nm) of the initial synthetic sample by arabinogalactan. Also, a biogenic ferrihydrite sample (an average particle size of 2-nm) with a natural organic coating was studied and it has the weakest magnetic interparticle interactions among of all the samples. Relaxation times of the particle’s magnetic moment were determined by the data of static and dynamic magnetic susceptibilities and from analysis of 57Fe Mössbauer spectrometry. Based on the temperature dependences of the relaxation times, it has been concluded that the predominantly collective processes of freezing of the particle magnetic moments occur under the action of the magnetic interparticle interactions. It is shown that an important role in these processes is played by a magnetic subsystem of the surface spins of the particles. The effect of the interplay between the surface spin and magnetic moment subsystems on the static magnetic properties (low-temperature magnetic hysteresis loops) and the parameters of the microwave absorption line under the magnetic resonance conditions is discussed.

A photochromic trinuclear dysprosium(iii) single-molecule magnet with two distinct relaxation processes.

Multifunctional molecules responsive to light are highly desired as components for the construction of remotely controlled nanodevices. Here we present a DyIII single molecule magnet (SMM) comprising dithienylethene (dte) photochromic bridging ligands in the form of a pyridine (py) derivative: 1,2-bis((2-methyl-5-pyridyl)thie-3-yl)perfluorocyclo-pentene (dtepy). The title trinuclear compound {[DyIII(BHT)3]3(dtepy)2}·4C5H12 (1) was synthesized by combining the low-coordinate dysprosium complexes DyIII(BHT)3 (BHT = 2,6-di-tert-butyl-4-methylphenolate) with dtepy bridging ligands in the 'open' form using n-pentane as a completely inert solvent. The trinuclear molecule comprises two different DyIII centers due to its quasi-linear geometry: a central trigonal bipyramidal DyIII ion and two peripheral ones with an approximate trigonal pyramidal geometry. Thanks to that, 1 shows two types of SMM behavior which is slightly affected by the photoisomerization of the photochromic dtepy bridges. The impact of the photoisomerization on the magnetization dynamics was studied by means of alternating current (AC) magnetic susceptibility measurements for the 'open' and 'closed' forms of the molecules. The changes between the 'open' and 'closed' isomers were further investigated by IR and UV-vis spectroscopy, suggesting the co-existence of the ligand-related photochromism and single-molecule magnet behavior in 1. However, the powder X-ray diffraction studies indicate loss of structural order in the first photoisomerization step preventing in-depth studies.

Photoluminescent and Magnetic Properties of Mononuclear Lanthanide-Based Compounds Containing the Zwitterionic Form of 4-Picolinic Acid as a Ligand

A series of mononuclear lanthanide-based coordination compounds was obtained under mild synthetic conditions and fully characterized. Single-crystal X-ray diffraction reveals six isomorphic compounds of type [Ln(NO3)(4picH)2(H2O)4](NO3)2 (Ln3+ = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Er (6)), in which 4picH is the zwitterionic form of the 4-picolinic acid. Except for compounds 3 and 6, a study into the emissive properties of the compounds was carried out, revealing a ligand-sensitized lanthanide-characteristic luminescence. Compounds 2 and 4 are candidates for luminescent probes in solution. At the same time, the chromaticity data for 5 revealed a potential white-light emitter with a correlated color temperature (CCT) value of 6570 K. Alternating current (AC) magnetic susceptibility measurements, supported by theoretical calculations, showed a field-induced slow relaxation of the magnetization and a single-ion magnet behavior for compound 5.

Approaching the 1000 K energy barrier in high coordinate lanthanide single-ion magnets: Increasing Ueff in the [Dy(Tp2-py)F]+ moiety with tetrahydrofuran.

Using the existing architecture of [Dy(Tp2-py)F]+ that supports a terminal Dy-F bond, the synthesis and isolation of [Dy(Tp2-py)F(THF)2](PF6) and its diamagnetic yttrium analogue have been achieved. Alternating current magnetic susceptibility studies show an increased effective energy barrier of Ueff = 661(6) cm-1 (951(8) K), the highest yet reported for a high coordinate (n > 8) lanthanide single-ion magnet.

The Relationship between Annealing Temperatures and Surface Roughness in Shaping the Physical Characteristics of Co40Fe40B10Dy10 Thin Films

Co40Fe40B10Dy10 thin films, with thicknesses varying between 10 nm and 50 nm, were grown on a Si(100) substrate. Subsequently, they underwent a 1 h annealing process in an Ar atmosphere at temperatures of 100 °C, 200 °C, and 300 °C. The oxide characteristic peaks of Dy2O3(440), Co2O3(422), and Co2O3(511) were revealed by X-ray diffraction (XRD). The low-frequency alternating current magnetic susceptibility (χac) decreases with frequency. Due to thickness and the anisotropy of the magnetic crystal, the maximum χac and saturation magnetization values rise with thicknesses and annealing temperatures. As the thickness and heat treatment temperature rise, the values for resistivity and sheet resistance tend to fall. The results of atomic force microscopy (AFM) and magnetic force microscopy (MFM) show that average roughness (Ra) lowers as the annealing temperature increases, and the distribution of strip-like magnetic domain becomes more visible. As thickness and annealing temperature increase, there is a corresponding rise in surface energy. Nano-indentation testing shows that hardness initially decreases from 10 nm to 40 nm, followed by an increase at 50 nm. Notably, annealing at 300 °C leads to a significant hardening effect, marking the highest level of hardness observed. Young’s modulus increased as thicknesses and annealing temperatures increased. The magnetic, electric, and adhesive characteristics of CoFeBDy films are highly dependent on surface roughness at various annealing temperatures.

Surface Roughness-Induced Changes in Important Physical Features of CoFeSm Thin Films on Glass Substrates during Annealing.

Co60Fe20Sm20 thin films were deposited onto glass substrates in a high vacuum setting. The films varied in thickness from 10 to 50 nm and underwent annealing processes at different temperatures: room temperature (RT), 100, 200, and 300 °C. Our analysis encompassed structural, magnetic, electrical, nanomechanical, adhesive, and optical properties in relation to film thickness and annealing temperature. X-ray diffraction (XRD) analysis did not reveal characteristic peaks in Co60Fe20Sm20 thin films due to insufficient growth-driving forces. Electrical measurements indicated reduced resistivity and sheet resistance with increasing film thickness and higher annealing temperatures, owing to hindered current-carrier transport resulting from the amorphous structure. Atomic force microscope (AFM) analysis showed a decrease in surface roughness with increased thickness and annealing temperature. The low-frequency alternating current magnetic susceptibility (χac) values increased with film thickness and annealing temperature. Nanoindentation analysis demonstrated reduced film hardness and Young's modulus with thicker films. Contact angle measurements suggested a hydrophilic film. Surface energy increased with greater film thickness, particularly in annealed films, indicating a decrease in contact angle contributing to this increase. Transmittance measurements have revealed intensified absorption and reduced transmittance with thicker films. In summary, the surface roughness of CoFeSm films at different annealing temperatures significantly influenced their magnetic, electrical, adhesive, and optical properties. A smoother surface reduced the pinning effect on the domain walls, enhancing the χac value. Additionally, diminished surface roughness led to a lower contact angle and higher surface energy. Additionally, smoother surfaces exhibited higher carrier conductivity, resulting in reduced electrical resistance. The optical transparency decreased due to the smoother surface of Co60Fe20Sm20 films.

Studying the Effects of Annealing and Surface Roughness on Both the Magnetic Property and Surface Energy of Co60Fe20Sm20 Thin Films on Si(100) Substrate

In this study, Co60Fe20Sm20 alloy was employed for sputter deposition onto Si(100) substrate within a high vacuum environment, and subsequent thermal treatment was conducted using a vacuum annealing furnace. Thorough measurements and analyses were carried out to evaluate how various film thicknesses and annealing temperatures affect the material. The investigations encompassed observations of structural and physical properties, magnetic traits, mechanical behavior, and material adhesion. The results from the four-point probe measurements clearly demonstrate a trend of decreasing resistivity and sheet resistance with increasing film thickness and higher annealing temperature. Analysis through atomic force microscopy (AFM) shows that heightened annealing temperature corresponds to decreased surface roughness. Furthermore, when analyzing low-frequency alternating current magnetic susceptibility (χac), it became evident that the maximum magnetic susceptibility value consistently rises with increased film thickness, regardless of the annealing temperature. Through magnetic force microscopy (MFM) observations of magnetic domain images in the films, it became apparent that there was a noticeable reduction in the brightness contrast of the magnetic domains. Furthermore, nanoindentation analysis reveals a clear trend. Elevating the film thickness leads to a reduction in both hardness and Young’s modulus. Contact angles range between 67.7° and 83.3°, consistently under 90°, highlighting the hydrophilic aspect. Analysis of surface energy demonstrates an escalation with increasing film thickness, and notably, annealed films exhibit a substantial surge in surface energy. This signifies a connection between the reduction in contact angle and the observed elevation in surface energy. Raising the annealing temperature causes a decline in surface roughness. To summarize, the surface roughness of CoFeSm films at different annealing temperatures significantly impacts their magnetic, electrical, and adhesive properties. A smoother surface reduces the pinning effect on domain walls, thus enhancing the χac value. Furthermore, diminished surface roughness leads to a decline in the contact angle and a rise in surface energy. Conversely, rougher surfaces exhibit higher carrier conductivity, contributing to a reduction in electrical resistance.

Slow Magnetization Relaxation in a Family of Triangular {CoIII 2 LnIII } Clusters: The Effect of Diamagnetic CoIII Ions on the LnIII Magnetic Dynamics.

The first use of the Schiff base chelate N-naphthalidene-o-aminophenol (naphH2 ) in Co/Ln chemistry has afforded a family of isostructural [CoIII 2 LnIII (OMe)2 (naph)2 (O2 CMe)3 (MeOH)2 ] (Ln=Tb, Dy and Er) complexes, revealing a rare {CoIII 2 Ln(μ3 -OMe)}8+ triangular core composed of two diamagnetic CoIII ions and a 4f-ion with slightly distorted square antiprismatic geometry. Alternating current (ac) magnetic susceptibility studies revealed that {Co2 Dy}, and its magnetic diluted analogue {Co2 Dy0.05 Y0.95 }, behave as mononuclear single-molecule magnets (SMMs) with similar energy barriers for the magnetization reversal, Ueff , of ~85-90 K. SMM properties were also detected for {Co2 Er}, with the compound exhibiting a Ueff of 18.7 K under an applied magnetic field of 800 Oe. To interpret the experimental magnetic results, ab initio CASSCF/RASSI-SO and DFT calculations were performed as a means of exploring the single-ion characteristics of LnIII ions and comprehend the role of the diamagnetic CoIII ions in the magnetization relaxation of the three heterometallic compounds.

Thickness, Annealing, and Surface Roughness Effect on Magnetic and Significant Properties of Co40Fe40B10Dy10 Thin Films.

In this study, Co40Fe40B10Dy10 thin films were deposited using a direct current (DC) magnetron sputtering technique. The films were deposited on glass substrates with thicknesses of 10, 20, 30, 40, and 50 nm, and heat-treated in a vacuum annealing furnace at 100, 200, and 300 °C. Various instruments were used to examine and analyze the effects of roughness on the magnetic, adhesive, and mechanical properties. From the low frequency alternating current magnetic susceptibility (χac) results, the optimum resonance frequency is 50 Hz, and the maximum χac value tends to increase with the increase in the thicknesses and annealing temperatures. The maximum χac value is 0.18 at a film thickness of 50 nm and an annealing temperature of 300 °C. From the four-point probe, it is found that the resistivity and sheet resistance values decrease with the increase in film deposition thicknesses and higher annealing temperatures. From the magnetic force microscopy (MFM), the stripe-like magnetic domain distribution is more obvious with the increase in annealing temperature. According to the contact angle data, at the same annealing temperature, the contact angle decreases as the thickness increases due to changes in surface morphology. The maximal surface energy value at 300 °C is 34.71 mJ/mm2. The transmittance decreases with increasing film thickness, while the absorption intensity is inversely proportional to the transmittance, implying that the thickness effect suppresses the photon signal. Smoother roughness has less domain pinning, more carrier conductivity, and less light scattering, resulting in superior magnetic, electrical, adhesive, and optical performance.

Rare Nuclearities and Unprecedented Structural Motifs in Manganese Cluster Chemistry from the Combined Use of Di-2-Pyridyl Ketone with Selected Diols

The combined use of di-2-pyridyl ketone ((py)2CO) with various diols in Mn cluster chemistry has afforded five new compounds, namely, [Mn11O2(OH)2{(py)2CO2}5(pd)(MeCO2)3(N3)3(NO3)2(DMF)4](NO3)∙2DMF∙H2O (1∙2DMF∙H2O), [Mn11O2(OH)2{(py)2CO2}5(mpd)(MeCO2)3(N3)3(NO3)2(DMF)4](NO3) (2), [Mn12O4(OH)2{(py)2CO2}4(mpd)2(Me3CCO2)4(NO3)4(H2O)6](NO3)2∙2MeCN (3∙2MeCN), [Mn4(OMe)2{(py)2C(OMe)O}2(2-hp)2(NO3)2(DMF)2] (4), and [Mn7{(py)2CO2}4(2-hp)4(NO3)2(DMF)2](ClO4)∙DMF (5∙DMF) ((py)2CO22− and (py)2C(OMe)O− = gem-diol and hemiketal derivatives of di-2-pyridyl ketone, pdH2 = 1,3-propanediol, mpdH2 = 2-metly-1,3-propanediol, 2-hpH2 = 2-(hydroxymethyl)phenol). Complexes 1 and 2 are isostructural, possessing an asymmetric [MnIII5MnII6(μ4-O)(μ3-O)(μ3-OH)(μ-OH)(μ3-OR)2(μ-OR)10(μ-N3)]8+ core. Compound 3 is based on a multilayer [MnIII8MnII4(μ4-O)2(μ3-O)2(μ3-OH)2(μ-OR)12]10+ core, while complex 4 comprises a defective dicubane core. The crystal structure of 5 reveals that it is based on an unusual non-planar [MnIII5MnII2(μ-OR)12]7+ core with a serpentine-like topology. Direct current (dc) magnetic susceptibility studies revealed the presence of dominant antiferromagnetic exchange interactions in complex 3, while ferromagnetic coupling between the Mn ions was detected in the case of compound 5. Fitting of the magnetic data for complex 4 revealed weak antiferromagnetic interactions along the peripheral MnII∙∙∙MnIII ions (Jwb = −0.33 (1) cm−1) and ferromagnetic interactions between the central MnIII∙∙∙MnIII ions (Jbb = 6.28 (1) cm−1).

Comprehensive magnetic analysis of the tephras in Middle-Late Pleistocene loess records of Serbia, and implications for tephra identification, correlation and loess chronology

Tephras are highly valuable for achieving precise chronologies and secure correlations for sedimentary sequences. Rock magnetic investigations provide a simple, rapid tool for tephra identification especially for weathered tephra, cryptotephra (hidden tephra), thin and dispersed distal tephra. But so far, the most diagnostic magnetic properties for tephra identification and for differentiation of specific tephras are still uncertain. Three laterally continuous and representative tephras/cryptotephras embedded in Serbian loess deposits provide a rare opportunity to explore application of magnetic approaches in tephrostratigraphy. Systematic rock magnetic and petrographic comparison of tephra and its host loess reveal that the characteristic magnetic mineral of the studied tephras is moderate-Ti titanomagnetite of magmatic origin, with a dominant magnetic grain size of non-interacting single domain (SD) and pseudo-single domain (PSD) state. We identify the most diagnostic magnetic properties for tephra identification in loess and many other sediments. The Curie temperature of titanomagnetite is the most diagnostic property of tephras. A low-temperature alternating current (AC) magnetic susceptibility peak at ∼20–100 K is a sensitive indicator of coarse-grained titanomagnetite. SIRM-χfd and χARM-χfd plots can easily differentiate tephras from loess-paleosol sequences and possibly other pedogenesis-influenced sediments. Furthermore, our results suggest Curie temperatures can be a promising tool of regional tephra correlation. Our magnetic evidence and mineral composition analysis support the same origin of Tephra-L5 as Tephra-L4 from Alban Hills Volcanic District, possibly from the ∼457 ka eruption, which would promote a robust chronostratigraphic model of Danube loess.

Field-Induced Single-Ion Magnet Behavior in Nickel(II) Complexes with Functionalized 2,2':6'-2″-Terpyridine Derivatives: Preparation and Magneto-Structural Study.

Two mononuclear nickel(II) complexes of the formula [Ni(terpyCOOH)2](ClO4)2∙4H2O (1) and [Ni(terpyepy)2](ClO4)2 MeOH (2) [terpyCOOH = 4'-carboxyl-2,2':6',2″-terpyridine and terpyepy = 4'-[(2-pyridin-4-yl)ethynyl]-2,2':6',2″-terpyridine] have been prepared and their structures determined by single-crystal X-ray diffraction. Complexes 1 and 2 are mononuclear compounds, where the nickel(II) ions are six-coordinate by the six nitrogen atoms from two tridentate terpy moieties. The mean values of the equatorial Ni-N bond distances [2.11(1) and 2.12(1) Å for Ni(1) at 1 and 2, respectively, are somewhat longer than the axial ones [2.008(6) and 2.003(6) Å (1)/2.000(1) and 1.999(1) Å (2)]. The values of the shortest intermolecular nickel-nickel separation are 9.422(1) (1) and 8.901(1) Å (2). Variable-temperature (1.9-200 K) direct current (dc) magnetic susceptibility measurements on polycrystalline samples of 1 and 2 reveal a Curie law behavior in the high-temperature range, which corresponds to magnetically isolated spin triplets, the downturn of the χMT product at lower temperatures being due to zero-field splitting effects (D). Values of D equal to -6.0 (1) and -4.7 cm-1 (2) were obtained through the joint analysis of the magnetic susceptibility data and the field dependence of the magnetization. These results from magnetometry were supported by theoretical calculations. Alternating current (ac) magnetic susceptibility measurements of 1 and 2 in the temperature range 2.0-5.5 K show the occurrence of incipient out-phase signals under applied dc fields, a phenomenon that is characteristic of field-induced Single-Molecule Magnet (SMM) behavior, which herein concerns the 2 mononuclear nickel(II) complexes. This slow relaxation of the magnetization in 1 and 2 has its origin in the axial compression of the octahedral surrounding at their nickel(II) ions that leads to negative values of D. A combination of an Orbach and a direct mechanism accounts for the field-dependent relation phenomena in 1 and 2.

Schiff Bases Functionalized with T-Butyl Groups as Adequate Ligands to Extended Assembly of Cu(II) Helicates.

The study of the inherent factors that influence the isolation of one type of metallosupramolecular architecture over another is one of the main objectives in the field of Metallosupramolecular Chemistry. In this work, we report two new neutral copper(II) helicates, [Cu2(L1)2]·4CH3CN and [Cu2(L2)2]·CH3CN, obtained by means of an electrochemical methodology and derived from two Schiff-based strands functionalized with ortho and para-t-butyl groups on the aromatic surface. These small modifications let us explore the relationship between the ligand design and the structure of the extended metallosupramolecular architecture. The magnetic properties of the Cu(II) helicates were explored by Electron Paramagnetic Resonance (EPR) spectroscopy and Direct Current (DC) magnetic susceptibility measurements.

A tetranuclear Er(III)-based cluster with bifunctional properties: Efficient conversion of CO2 and slow magnetic relaxation behavior

A new Er4 cluster [Er4(NO3)2(acac)4(L)2(CH3OH)2]·2CH3CN (1) (H4L = (E)-2-(hydroxymethyl)-2-(((2-hydroxynaphthalen-1-yl)methylene)amino)propane-1,3-diol, and Hacac = acetylacetone) were synthesized by employing a polydentate Schiff-base ligand (H4L) and a β-diketonate co-ligand and further characterized structurally. Alternating current (ac) magnetic susceptibility measurements indicated that cluster 1 shows slow relaxation of magnetization behavior. More importantly, cluster 1 shows high catalytic activity of the cycloaddition reaction of CO2 and epichlorohydrin under mild conditions; and cluster 1 as heterogenous catalyst can be reused at least three times without any obvious loss in catalytic activity. It is worth mentioning that cluster 1 is a rare bifunctional Ln(III)-based material for both molecular based magnetic material and heterogenous catalyst.

Supramolecular Co(II) complexes based on dithiolate and dicarboxylate ligands: Crystal structures, theoretical studies, magnetic properties, and catalytic activity studies in photocatalytic hydrogen evolution

Two supramolecular Co(II)-based coordination compounds have been harvested from dithiolate and dicarboxylate ligands. They have been structurally characterized by FT-IR, elemental analysis, and single crystal X-ray diffraction. Salt 1 consists of two ([tris (2-aminoethyl) amine Co] 1,1-dicyano-2,2-ethylenedithiolate)+ per thiosulphate ion linked through intermolecular hydrogen bonds. Compound 2, (pyridine-2,6-dicarboxylate)2Co-5H2OCo).2H2O, is stabilized by intramolecular O−H···O hydrogen bonds, building ribbons that propagate along the [100] direction in the crystals. From HS analysis, it is observed that the major non-covalent interactions present in 1 are C−H···O, N−H···N, N−H···S, and N−H···O hydrogen bonds, which play an important role in stabilizing the crystal structure. In 2, out of all the non-covalent interactions, O···H/H···O interactions have major contributions to stabilize the crystal structure. Theoretical investigation on the molecular structures of the crystals also revealed that the major stabilizing factor for 1 is H-bonding along with π-π stacking while that for 2 is co-ordinate bond between water and cobalt(II) ion. Direct current variable-temperature magnetic susceptibility measurements carried out on polycrystalline samples of 1 and 2 in the temperature range of 1.8–300 K shows the presence of magnetic anisotropy of the cobalt(II) ion in 1 and weak intermolecular exchange in 2. Further, both the compounds 1 and 2 are found to be highly efficient water reduction catalysts in terms of per Co turn-over-numbers at lower concentrations.