Magnetic Field Dependence Research Articles

Magnetic field dependence of the para-ortho conversion rate of molecular hydrogen in SABRE experiments

The use of parahydrogen – the isomer of molecular hydrogen with zero nuclear spin – is important for promising and actively developing methods for spin hyperpolarization of nuclei called parahydrogen induced polarization (PHIP). However, the dissolved parahydrogen in PHIP experiments quickly loses its spin order, resulting in the formation of orthohydrogen and reduction of the overall nuclear polarization of the substrate. This process is due to the difference of chemical shifts of hydride protons, as well as spin–spin couplings between nuclei, in the intermediate catalytic complexes, and it has not been rigorously explained so far. We proposed a new experimental technique based on magnetic field cycling for measuring the rate of molecular hydrogen para–ortho conversion in solution and applied it for non-hydrogenative PHIP Signal Amplification By Reversible Exchange (SABRE) experiments. The para–ortho conversion rate was measured over a wide range of magnetic field from 0.5 mT to 9.4 T. It was found that the conversion rate strongly depends on the magnetic field in which the reaction occurs, as well as on the concentrations of reactants. The rate decreases with increasing the concentration of pyridine ligand and increases with increasing the concentration of iridium catalyst. The model, which takes into account the reversible exchange of molecular hydrogen with the catalyst, nuclear spin–spin interaction of hydride protons with nuclei of ligands within catalytic complex and nuclear Zeeman interactions, qualitatively describes the experimental data. Two types of complexes with different spin system symmetry contribute to the molecular hydrogen conversion. In asymmetric complexes possessing hydride protons with different chemical shifts due to the presence of chlorine anion ligand the para–ortho conversion rate increases with magnetic field, while for symmetric complexes this mechanism is not operable. In the magnetic field where level anti-crossing occurs the resonant feature for the rate of para–ortho conversion is found. The results of this work can be utilized for finding the optimal conditions for obtaining the maximum hyperpolarization in the experiments employing parahydrogen.

Flux creep regimes and vortex phase diagram in β-FeSe single crystals

We analyze the relationship between critical current densities (JC) and flux creep rates (S) in β-FeSe single crystals. This analysis was based on magnetization measurements. Additionally, we establish correlations with the recently reported magnetic field-induced geometrical deformation of the vortex lattice, transitioning from hexagonal to square shape due to a rhombic distortion [A. V. Putilov et al. Phys. Rev 99 (2019) 144514]. The results show that the magnetic field dependence of Jc displays distinct regimes, which is reflected by changes in S. The vortex dynamics is analyzed within the framework of the collective creep theory. S is characterized by low pinning energies and glassy exponents according to the expectation for small-bundles at low temperatures and magnetic fields where a hexagonal vortex lattice was reported. Conversely, we observe a systematic increase in S, resembling a shift from small to large vortex bundles, at magnetic fields corresponding to the rhombic distortion. Last, the relaxation rates exhibit significant values for magnetic fields where a square vortex lattice is expected, suggesting a potential crossover from elastic to plastic creep. Our findings highlight a direct relationship between vortex lattice deformations and a decrease in vortex pinning related to vortex-defect interactions.

The Crystal Structure and Physicochemical Properties of New Complexes Containing a CuII-LnIII-CuII Core

Three new cationic complexes, [Cu4Tb2(H2L)4(NO3)4(H2O)3](NO3)2·5.5H2O·2MeOH (1), [Cu4Ho2(H2L)4(NO3)4(H2O)3](NO3)2·7.5H2O (2), and [Cu4Er2(H2 L)4(NO3)4(H2O)3](NO3)2·7H2O·3MeOH (3), were synthesized and studied using elemental and TG/DTG/DSC analyses, single-crystal X-ray diffraction, and magnetic measurements. The structure analysis showed that 1–3 crystallize as (NO3)-bridged compounds and that the lanthanide(III) ion acts as a joint connecting two [CuH2L] coordination units. In each heterotrinuclear unit, an asymmetry in the degree of planarity of the bridging CuO2Ln fragments is observed. The CuII ions are five- and six-coordinate, with distorted square pyramidal and octahedral geometry, respectively, whereas the LnIII ions are nine-coordinate. The solvates 1–3 are stable at room temperature, and their desolvation process is consistent with the loss of water and/or methanol molecules. The temperature dependence of the magnetic susceptibility and the field-dependent magnetization indicate the weak ferromagnetic interaction between the paramagnetic centers CuII and TbIII/HoIII 1 and 2.

Highly efficient magnetically separable SrFe12O19 for photo-assisted oxidation of benzylic alcohol derivatives under visible light

The selective oxidation of the Cα−OH group of benzylic alcohols is a crucial process for the conversion of lignin into useful products. In this study, we describe the synthesis and characterization of magnetic strontium hexaferrite, SrFe12O19. The SrFe12O19 nano-powder was produced through coprecipitation at a pH level of 10. The catalyst has been studied using various methods such as X-ray diffraction (XRD), scanning electron microscopy (SEM) combined with energy-dispersive X-ray analysis (EDX), UV–vis diffuse reflectance spectroscopy (DRS), and magnetic field dependence measurements. The study aimed to evaluate the photocatalytic performance of SrFe12O19 in selective oxidation of benzylic alcohols and degradation of methylene blue under visible light. Additionally, the magnetic properties of the catalyst were also investigated. Magnetic properties were also investigated. M-SrFe12O19 with a band near 2 eV, showed excellent photocatalytic degradation performance at ca. 90% of MB under visible light. The photocatalytic degradation activity was evaluated for three cycles, and the results demonstrate that it maintains its photodegradation potency, with significant photo-degradation conversion of 89%, 87%, and 84%. The experiment clearly demonstrated that the reaction kinetics followed a pseudo-first order. The oxidation of benzyl alcohol (BzOH) was successfully carried out over SrFe12O19 in the presence of hydrogen peroxide, a highly effective green oxidant, under visible light. Notably, the experiment results showed a maximum conversion of BzOH, reaching approximately 70%, with absolute selectivity towards benzaldehyde (BzCHO). Furthermore, the yield of aldehyde increases according to the Hammett constant, with the highest yield being obtained for 2-hydroxybenzaldehyde (σ = −0.37). The synthesized M-SrFe12O19 material shows potential as an eco-friendly method for lignin valorization.

A computational approach to predict and enhance the sensitivity of X-ray resonant magnetic reflectometry to the magnetic behavior of deeply buried interfaces

In the present work a computational approach is applied to model and predict the results of X-ray resonant magnetic reflectometry – a non-destructive synchrotron-based technique to probe chemical composition, crystallographic environment and magnetization in multilayer epitaxial heterostructures with nanoscale depth resolution. The discussed 2D mapping approach is a step forward with respect to conventional resonant X-ray reflectometry and consists of collecting a fine step array of reflected intensity as a function of grazing angle and photon energy across the absorption edge of a particular chemical element. With the use of circularly polarized photons the method can be extended to magnetic systems to produce a map of dichroic reflectance directly related to the magnetization profile of the heterostructure. Studying the magnetic field dependence of dichroic reflectance maps can provide valuable information on the magnetization reversal of individual sublayers of a multilayer heterostructure. In the present paper modeling is performed for a bilayer system mimicking the behavior of a 30 nm ɛ-Fe2O3 thin film that is known to exhibit a pronounced two-component magnetic hysteresis. A technique to find optimal energy/angle combinations in order to sense magnetization of individual sublayers is proposed. Also discussed is the advantage of heavy-element capping, which leads to a substantial increase of the dichroic intensity oscillation contrast in the pre-edge region where the sensitivity to the magnetic behavior of the deeply buried interfaces is most pronounced.

Switchable Wettability States of a Ferrofluid Droplet atop a Hydrophobic Interface.

Magnetically tuned soft machines offer great promise in performing a wide variety of programmable tasks via their dynamic shape adaptation and alteration. Despite dramatic recent advancements in this regard, selective reconfiguration of the wetting behavior of a ferrofluid droplet atop a hydrophobic interface adapted as a magnetically modulated micromachine remained elusive when the applied field intensity exceeds the saturation magnetization. Here we unveil a strategy to unsettle this perspective by harnessing a magnetic field-dependent magnetization phenomenon that may be exploited exclusively to arrive at highly controllable dynamic switchable wetting states of ferrofluid droplets, including the realization of wide ranges of contact angles for a given applied magnetic field. We arrive at a physical law from the resulting interplay of forces that quantifies the time dependence of the contact angle variation for a given magnetic field. Substantiated by experimental findings, our multiphysics-based simulations further evidence the possibilities of realizing switchable wetting states of soft magnetic matter over a wide range of physical parameters, delving into this principle. Disrupting the established notion of a trivially unique wetting phenomenon as governed by the droplet-substrate combination and the applied field alone, this paradigm may thus benefit a wide variety of practical applications, ranging from digital microfluidics to recombination chemistry.

Estimation of Heisenberg exchange interaction in rigid photoexcited chromophore-radical compound by transient EPR.

The magnetic field dependence of the spin polarization in a photoexcited rigid chromophore-radical conjugate is theoretically investigated. The excitation of the chromophore-radical conjugate often populates the metastable doublet and quartet states formed by the interactions of the unpaired electrons of the triplet chromophore and the radical. The intensities of the +1/2 ↔ - 1/2 transitions of the doublet and quartet manifolds are sensitive to the ratio jω = 3J/ω0 between the triplet-doublet exchange interaction J and the Zeeman energy ω0. It is shown that the analytical expressions of these intensities previously found for the triplet mechanism of the initial spin polarization can be expanded and applied to a broader class of compounds that may have other intersystem crossing pathways of the depopulation of the excited singlet state of the chromophore. It is also shown that the exchange interaction can be evaluated not only by comparing the electron paramagnetic resonance spectra obtained in different microwave frequency bands but also by comparing the data obtained in the same microwave band but with a shift of the frequency of the resonator. The results obtained broaden the potential applications of the previously proposed approach for analyzing the correlation between the exchange coupling and the distance separating the radical and the chromophore spins, as well as the structure of the bridge connecting their fragments.

Tuning the superconducting performance of YBa2Cu3O7-δ films through field-induced oxygen doping.

The exploration of metal-insulator transitions to produce field-induced reversible resistive switching effects has been a longstanding pursuit in materials science. Although the resistive switching effect in strongly correlated oxides is often associated with the creation or annihilation of oxygen vacancies, the underlying mechanisms behind this phenomenon are complex and, in many cases, still not clear. This study focuses on the analysis of the superconducting performance of cuprate YBa2Cu3O7-δ (YBCO) devices switched to different resistive states through gate voltage pulses. The goal is to evaluate the effect of field-induced oxygen diffusion on the magnetic field and angular dependence of the critical current density and identify the role of induced defects in the switching performance. Transition electron microscopy measurements indicate that field-induced transition to high resistance states occurs through the generation of YBa2Cu4O7 (Y124) intergrowths with a large amount of oxygen vacancies, in agreement with the obtained critical current density dependences. These results have significant implications for better understanding the mechanisms of field-induced oxygen doping in cuprate superconductors and their role on the superconducting performance.

External Magnetic Fields of Powerful Generators

Results of the magnetic field factory measurements near the surface of turbogenerator housings within the wide power range at no-load and short circuit conditions are presented. Presented also are the results of measurements of the external magnetic fields under the conditions of direct load with overexcitation and underexcitation. The analysis of the external magnetic fields dependence upon the rated power, electromagnetic loads, design features and efficiency of the internal magnetic fields shielding by means of the turbogenerator housing and end shields was conducted.

Quantum dipole interactions and transient hydrogen bond orientation order in cells, cellular membranes and myelin sheath: Implications for MRI signal relaxation, anisotropy, and T1 magnetic field dependence.

Despite significant impact on the study of human brain, MRI lacks a theory of signal formation that integrates quantum interactions involving proton dipoles (a primary MRI signal source) with brain intricate cellular environment. The purpose of the present study is developing such a theory. We introduce the Transient Hydrogen Bond (THB) model, where THB-mediated quantum dipole interactions between water and protons of hydrophilic heads of amphipathic biomolecules forming cells, cellular membranes and myelin sheath serve as a major source of MR signal relaxation. The THB theory predicts the existence of a hydrogen-bond-driven structural order of dipole-dipole connections within THBs as a primary factor for the anisotropy observed in MRI signal relaxation. We have also demonstrated that the conventional Lorentzian spectral density function decreases too fast at high frequencies to adequately capture the field dependence of brain MRI signal relaxation. To bridge this gap, we introduced a stretched spectral density function that surpasses the limitations of Lorentzian dispersion. In human brain, our findings reveal that at any time point only about 4% to 7% of water protons are engaged in quantum encounters within THBs. These ultra-short (2 to 3 ns), but frequent quantum spin exchanges lead to gradual recovery of magnetization toward thermodynamic equilibrium, that is, relaxation of MRI signal. By incorporating quantum proton interactions involved in brain imaging, the THB approach introduces new insights on the complex relationship between brain tissue cellular structure and MRI measurements, thus offering a promising new tool for better understanding of brain microstructure in health and disease.

Pauli blockade catalogue and three- and four-particle Kondo effect in bilayer graphene quantum dots

Pauli blockade is a fundamental quantum phenomenon that also serves as a powerful tool for qubit manipulation and readout. While most systems exhibit a simple even-odd pattern of double-dot Pauli spin blockade due to the preferred singlet pairing of spins, the additional valley degree of freedom offered by bilayer graphene greatly alters this pattern. Inspecting bias-triangle measurements at double-dot charge degeneracies with up to four electrons in each dot reveals a much richer double-dot Pauli blockade catalog with both spin and/or valley blockade. In addition, we use single-dot Kondo effect measurements to substantiate our understanding of the three- and four-particle state spectra by analyzing their magnetic field dependence. With high controllability and reported long valley- and spin-relaxation times, bilayer graphene is a rising platform for hosting semiconductor quantum dot qubits. A thorough understanding of state spectra is crucial for qubit design and manipulation, and the rich Pauli blockade catalog provides an abundance of qubit operational possibilities and opportunities to explore intriguing spin and valley physics. Published by the American Physical Society 2024

Experimental realization of CoFeRuSn quaternary Heusler alloy for room temperature spintronic applications

We synthesize CoFeRuSn equiatomic quaternary Heusler alloy using arc-melt technique and investigate its structural, magnetic, and transport properties. The room temperature powder x-ray diffraction analysis reveals that CoFeRuSn crystallizes in cubic crystal structure with small amount of DO3-disorder. The field dependence of magnetization shows non-zero but small hysteresis and saturation behavior up to room temperature, indicating soft ferromagnetic nature of CoFeRuSn. The magnetic moment estimated from the magnetization data is found to be 4.15 μB/f.u., which is slightly less than the expected Slater–Pauling rule. The deviation in the value of experimentally observed moment from the theoretical value might be due to small disorder in the crystal. The low temperature fit to electrical resistivity data shows the absence of quadratic temperature dependence of resistivity, suggesting half-metallic behavior of CoFeRuSn. The high Curie temperature and possible half-metallic behavior of CoFeRuSn make it a highly promising candidate for room temperature spintronic applications.

Coupled-cluster treatment of complex open-shell systems: the case of single-molecule magnets.

We investigate the reliability of two cost-effective coupled-cluster methods for computing spin-state energetics and spin-related properties of a set of open-shell transition-metal complexes. Specifically, we employ the second-order approximate coupled-cluster singles and doubles (CC2) method and projection-based embedding that combines equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) with density functional theory (DFT). The performance of CC2 and EOM-CCSD-in-DFT is assessed against EOM-CCSD. The chosen test set includes two hexaaqua transition-metal complexes containing Fe(II) and Fe(III), and a large Co(II)-based single-molecule magnet with a non-aufbau ground state. We find that CC2 describes the excited states more accurately, reproducing EOM-CCSD excitation energies within 0.05 eV. However, EOM-CCSD-in-DFT excels in describing transition orbital angular momenta and spin-orbit couplings. Moreover, for the Co(II) molecular magnet, using EOM-CCSD-in-DFT eigenstates and spin-orbit couplings, we compute spin-reversal energy barriers, as well as temperature-dependent and field-dependent magnetizations and magnetic susceptibilities that closely match experimental values within spectroscopic accuracy. These results underscore the efficiency of CC2 in computing state energies of multi-configurational, open-shell systems and highlight the utility of the more cost-efficient EOM-CCSD-in-DFT for computing spin-orbit couplings and magnetic properties of complex and large molecular magnets.

Influence of heat sintering on the physical properties of bulk La0.67Ca0.33MnO3 perovskite manganite: role of oxygen in tuning the magnetocaloric response.

The effect of heat treatments on bulk poly-crystalline La0.67Ca0.33MnO3 perovskite manganite is presented, to explore the possible enhancement in magnetocaloric performance. Samples were prepared via conventional solid-state reaction route with annealing and sintering at various temperatures. Detailed measurements of temperature-dependent and field-dependent magnetization were carried out to estimate the Curie point and order of magnetic transition. The increased sintering temperature results in a steep transition near the TC, and establishes the magnetic sensitivity as well as the active zone for substantial magnetocaloric performance, at about 168.2% for the LCM9 (sintered at 900 °C) sample. The cause for the significant improvement in the magnetic and magnetocaloric response is brought to light using detailed X-ray photoelectron spectroscopy (XPS) analysis, highlighting the role of oxygen in modifying the Mn3+/Mn4+ charge ratio. The maximum value of the isothermal magnetic entropy change for the optimized sample is found to be 6.4 J kg-1 K-1, achieved at 269 K, while temperature-averaged entropy change (TEC) values, TEC(ΔTH-C = 3 K) and TEC(ΔTH-C = 5 K), of 6 J kg-1 K-1 and 5.2 J kg-1 K-1, respectively, were obtained with a low magnetic field change of 20 kOe. The obtained isothermal entropy change at low field for the optimized La0.67Ca0.33MnO3 sample is higher than that of pure Gd and most oxide-based materials. The relative cooling power (RCP) value is around 93 J kg-1 (ΔH = 20 kOe). The order of the phase transition is examined with universal scaling; the scaled entropy change curves confirm the collapse onto a single curve for LCM9, asserting second-order character, whereas the breakdown of the curve with a dispersion relation (d) of 101.1% at Θ = -5 confirms the onset of intrinsic first-order nature in the case of the high-temperature-sintered samples. Calorimetry measurements show thermal hysteresis of 2.4 K and 7.1 K for LCM11 (sintered at 1100 °C) at ramp rates of 5 K min-1 and 10 K min-1, respectively, confirming the first-order nature of the magnetic transition.

How the spin state tunes the slow magnetic relaxation field dependence in spin crossover cobalt(II) complexes.

A novel family of cobalt(II) compounds with tridentate pyridine-2,6-diiminephenyl type ligands featuring electron-withdrawing substituents of general formula [Co(n-XPhPDI)2](ClO4)2·S [n-XPhPDI = 2,6-bis(N-n-halophenylformimidoyl)pyridine with n = 4 (1-3) and 3 (4); X = I (1), Br (2 and 4) and Cl (3); S = MeCN (1 and 2) and EtOAc (3)] has been synthesised and characterised by single-crystal X-ray diffraction, electron paramagnetic resonance, and static (dc) and dynamic (ac) magnetic measurements combined with theoretical calculations. The structures of 1-4 consist of mononuclear bis(chelating) cobalt(II) complex cations, [CoII(n-XPhPDI)2]2+, perchlorate anions, and acetonitrile (1 and 2) or ethyl acetate (3) molecules of crystallisation. This unique series of mononuclear six-coordinate octahedral cobalt(II) complexes displays both thermally-induced low-spin (LS)/high-spin (HS) transition and field-induced slow magnetic relaxation in both LS and HS states. A complete LS ↔ HS transition occurs for 1 and 2, while it is incomplete for 4, one-third of the complexes being HS at low temperatures. In contrast, 3 remains HS in all the temperature range. 1 and 2 show dual spin relaxation dynamics under the presence of an applied dc magnetic field (Hdc), with the occurrence of faster- (FR) and slower-relaxing (SR) processes at lower (Hdc = 1.0 kOe) and higher fields (Hdc = 2.5 kOe), respectively. On the contrary, 3 and 4 exhibit only SR and FR relaxations, regardless of Hdc. Overall, the distinct field-dependence of the single-molecule magnet (SMM) behaviour along with this family of spin-crossover (SCO) cobalt(II)-n-XPhPDI complexes is dominated by Raman mechanisms and, occasionally, with additional temperature-independent Intra-Kramer [LS or HS (D > 0)] or Quantum Tunneling of Magnetisation mechanisms [HS (D < 0)] also contributing.

Preparation and magnetic properties of MnFePSi-based glass-coated microwires

We prepared a Mn48Fe22P15Si15 glass-coated microwires (GCMWS) with metallic nucleus diameter, d = 11.2 μm and total diameter, D = 28.3 μm (geometrical aspect ratio d/D = 0.4) for the first time by using the Taylor–Ulitovsky Technique. This low-cost, single-step fabrication approach enabled the preparation of kilometers-long GCMWS from a few grams of low-cost components (Mn, Fe, P, and Si) for a variety of applications. The analysis of the magnetic measurements revealed a well-defined magnetic anisotropy in the whole temperature range. Moreover, relatively hard magnetic properties were observed for the temperature range of 5–400 K, where the average of coercivity, Hc ≈ 465 Oe. Notable magnetic field, H, and temperature dependencies of the magnetic properties were observed. Substantially irreversible magnetic behavior with a blocking temperatures Tb = 97 K at H = 1 kOe and Tb = 50 K at H = 5 kOe upon field cooling was observed. The modification in the magnetic properties of MnFePSi-glass-coated microwires is ascribed to the presence of various magnetic phases resulting from internal stresses induced by the glass coating. Moreover, the elevated Curie temperature (Tc &amp;gt; 400 K) observed in the investigated sample, makes this material as an appealing choice for several industrial applications.

Halide mediated modulation of magnetic interaction and anisotropy in dimeric Co(II) complexes.

The burgeoning interest in the field of molecular magnetism is to perceive the high magnetic anisotropy in different geometries of metal complexes and hence to draw a magneto-structural correlation. Despite a handful of examples to exemplify the magnetic anisotropy in various coordination geometries of mononuclear complexes, the magnetic anisotropies for two different coordination geometries are underexplored. Employing an appropriate synthetic strategy utilizing the ligand LH2 [2,2'-{(1E,1'E)-pyridine2,6-diyl-bis(methaneylylidine)}-bis(azaneylylidine)diphenol] and cobalt halide salts in a 1 : 2 stoichiometric ratio in the presence of triethylamine allowed us to report a new family of dinuclear cobalt complexes [CoII2X2(L)(P)(Q)]·S with varying terminal halides [X = Cl, P = CH3CN, Q = H2O, S = H2O (1), X = Br, P = CH3CN, Q = H2O, S = H2O (2), X = I, P = CH3CN, and Q = CH3CN (3)]. All these complexes are characterized through single crystal X-ray crystallography, which reveals their crystallization in the monoclinic system P21/n space group with nearly identical structural features. These complexes share vital components, including Co(II) centers, a fully deprotonated ligand [L]2-, halide ions, and solvent molecules. The [L]2- ligand contains two Co(II) centers, where phenolate oxygen atoms bridge the Co(II) centers, forming a Co2O2 four-membered ring. Co1 demonstrates a distorted pentagonal-bipyramidal geometry with axial positions for solvent molecules, while Co2 displays a distorted tetrahedral geometry involving phenolate oxygen atoms and halide ions. Temperature-dependent dc magnetic susceptibility measurements were conducted on 1-3 within a range of 2 to 300 K at 1 kOe. The χmT vs. T plots exhibit similar trends, with χmT values at 300 K higher than the spin-only value, signifying a significant orbital contribution. As the temperature decreases, χmT decreases smoothly in all the complexes; however, no clear saturation at low temperatures is observed. Field-dependent magnetization measurements indicate a rapid increase below 20 kOe, with no hysteresis and a low magnetic blocking temperature. DFT and CASSCF/NEVPT2 theoretical calculations were performed to perceive the magnetic interaction and single-ion anisotropies of Co(II) ions in various ligand-field environments.

A high-spin s-triazine linked fluorenyl radical polymer.

The syntheses of high-spin organic polymers have been a daunting task due to the highly reactive nature of organic radicals, especially when they are ferromagnetically coupled. In this paper, we report our approach to obtain high-spin organic polymers, in which a reasonably stable fluorenyl radical was employed as the primary radical unit, and s-triazine serves as the connector that facilitates ferromagnetic coupling between them. Initially, the diamagnetic polymer precursor was synthesized by cyclotrimerization of a cyano-monomer. Subsequently, the high-spin polymers were obtained by oxidizing corresponding anionic polymers using O2 (6) or I2 (7). The temperature-dependent magnetic moments, and field-dependent magnetization data obtained from SQUID measurements revealed ferromagnetic couplings between primary radical units, with coupling J = 7.5 cm-1 and 38.6 cm-1. The percentages of primary unit in the radical form are 29%, and 47% for 6 and 7, respectively. Notably, this marks the first reported instance of a high-spin fluorenyl radical polymer exhibiting ferromagnetic coupling.

Slow magnetic relaxation in a complex of photochromic spiropyran in a merocyanine form and cobalt(II) hexafluoroacetylacetonate.

The interaction between photochromic 8-methoxy-1',3',3'-trimethyl-6-nitro-spiro[chromene-2,2'-indole] (MNSP) and cobalt(II) hexafluoroacetylacetonate yields a deep red-violet solution due to the coordination-induced transition of MNSP from a colorless closed state to a colored open merocyanine (MC) form. The resulting complex {CoII(hfac)2·MNSP} (1) is obtained as crystals, and its structure at 250 K shows the coordination of two oxygen atoms from MNSP with CoII, forming a distorted octahedral surrounding around CoII. The unit cell of 1 contracts below 170 K by 5.5%, which is accompanied by shortening O-Co bonds and altering O-Co-O angles in the structure solved at 150 K. The χMT value of 3.06 emu K mol-1 at 300 K indicates the formation of high-spin CoII (S = 3/2) with a large orbital contribution characteristic of the octahedral surrounding. The contraction of the unit cell of 1 below 170 K provides a reversible 2.2% change of χMT in the 170-160 K range during heating and cooling regimes without hysteresis. The electron paramagnetic resonance signal of 1 was simulated with g-values of gx = 2.342, gy = 2.364, and gz = 2.084, and an isotropic g-factor of 2.267. The temperature-dependent χMT and field-dependent magnetization of 1 allow us to determine a positive zero-field splitting parameter of +20.1 cm-1. A study of the dynamic properties of 1 shows slow magnetic relaxation for CoII in a static field of 1000 Oe. Magnetic hysteresis loops were observed for 1 at 0.5 and 2 K; these loops are closed in the zero field region but opened at fields higher than ±100 and 700 Oe, respectively. The collapse of the loop is observed at 5 K. Excitation of the solution of 1 with green light decreases partially the intensity of the bands of the complex, whereas subsequent exposure of this solution to UV light partially restores these intensities.

LC-Photo-CIDNP hyperpolarization of biomolecules bearing a quasi-isolated spin pair: Magnetic-Field dependence via a rapid-shuttling device

Liquid-state low-concentration photochemically induced dynamic nuclear polarization (LC-photo-CIDNP) is an emerging technology tailored to enhance the sensitivity of NMR spectroscopy via LED- or laser-mediated optical irradiation. LC-photo-CIDNP is particularly useful to detect solvent-exposed aromatic residues (Trp, Tyr), either in isolation or within polypeptides and proteins. This study investigates the magnetic-field dependence of the LC-photo-CIDNP of Trp-α-13C-β,β,2,4,5,6,7-d7, a Trp isotopolog bearing a quasi-isolated 1Hα-13Cαspin pair (QISP). We employed a new rapid-shuttling side-illumination field-cycling device that enables ultra-fast (90–120 ms) vertical movements of NMR samples within the bore of a superconducting magnet. Thus, LC-photo-CIDNP hyperpolarization occurs at low field, while hyperpolarized signals are detected at high field (700 MHz). Resonance lineshapes were excellent, and the effect of several fields (1.18–7.08 T range) on hyperpolarization efficiency could be readily explored. Remarkably, unprecedented LC-photo-CIDNP enhancements ε ≅ 1,200 were obtained at 50 MHz (1.18 T), suggesting exciting avenues to hypersensitive LED-enhanced NMR in liquids at low field.