Slow Relaxation Research Articles

A rare case of a zero-field single-ion magnet in a cerium(III) pseudo-icosahedral complex.

The synthesis and structural characterisation of [Ln(Tp2-Fu)2]I (1-Ln; Ln = La, Ce, Pr, Nd) (Tp2-Fu = hydrotris(3-(2'-furyl)-pyrazol-1-yl)borate) have been reported as an isomorphous series adopting pseudo-icosahedral ligand field geometries. Continuous shape measurement (CShM) analyses on the crystal field environments of 1-Ln show the smallest values yet reported for complexes employing two hexadentate ligands (e.g. bis-scorpionate environments), with the smallest belonging to 1-La. Single-ion magnetism for 1-Ce, 1-Pr and 1-Nd was probed with ac magnetic susceptibility studies revealing slow magnetic relaxation for 1-Nd in applied magnetic fields and in zero-applied field for 1-Ce, which is a rare observation for Ce(III)-based single-ion magnets. The energy barrier to magnetic relaxation for 1-Ce was experimentally determined to be Ueff = 30(5) cm-1, which is comparable to that of other cerium-based single-molecule magnets in the literature, where these systems stablise the mJ = ±5/2 state and possess large energy gaps between the ground and first excited state that do not agree with the experimentally determined barrier.

SMM Behavior in Distorted Trigonal Bipyramidal and Tetrahedral Cobalt(II) Complexes Based on Tripodal Tetradentate Phenolic Amines

Four CoII complexes [Co(L1)(MeOH)]‧MeOH (1‧MeOH), [Co(L2)(MeOH)]‧MeOH (2‧MeOH), [Co(L3)(H2O)]‧MeOH (3‧MeOH) and [Co(L4)] (4), derived from tripodal tetradentate phenolic amine arms, H2L1‐4, were synthesized and structurally characterized. The complexes 1·MeOH, 2·MeOH and 3·MeOH displayed distorted trigonal bipyramidal geometry, whereas 4 exhibited distorted tetrahedral geometry, depending on the substituents at the phenolate rings and amine arm. The variation of the coordination geometries and interatomic parameters around the CoII center has an impact on the magnetic behavior of the compounds. The complexes show magnetic anisotropy (ZFS) of the MS = ± ½ and ± 3/2 sub‐levels, with D = 29.1(2), 22.7(1), 28.8(2) and 30.9(5) cm‐1 for 1‧MeOH, 2‧MeOH, 3‧MeOH and 4, respectively. The results obtained from ab initio CASSF calculations match well with the experimental data, revealing the origin of magnetic anisotropy. The dynamic ac magnetic investigation of the magnetic susceptibility revealed a slow magnetic relaxation behavior for 2·MeOH, 3·MeOH and 4. The field‐induced slow relaxation of the magnetization occurred through combination of Raman and Direct processes, depending on the variation in the coordination geometries imposed by the coordinated ligand and/or the interatomic parameters around the CoII center, which in turn have definite impact on the magnetic features of the compounds.

Phononic Resonant Relaxation in Magnetic Hysteresis of Single-Molecule Magnets

Abstract Lanthanide-based single-molecule magnets can exhibit broad magnetic hysteresis which basically manifests slow magnetic relaxation in strong magnetic fields. However, the cause of numerous nontrivial hysteresis behaviors remain debated. Here, we put forward two influential mechanisms: the activation of optical-phonon-mediated direct transitions within the ground-state doublet and resonant Raman process. These discoveries, coupled with the g-factor anisotropy, can account for observed hysteresis behaviors in the regimes of fast magnetic relaxation. Our findings substantially complement the recognized mechanisms used to interpret the magnetic hysteresis of single molecule magnets.

Quantifying Magnetic Anisotropy of Series of Five-Coordinate CoII Ions: Experimental and Theoretical Insights.

Stabilizing large easy-axis type magnetic anisotropy in molecular complexes is a challenging task, yet it is crucial for the development of information storage devices and applications in molecular spintronics. Achieving this requires a deep understanding of electronic structure and the relationships between structure and properties to develop magneto-structural correlations that are currently unexplored in the literature. Herein, a series of five-coordinate distorted square pyramidal CoII complexes [Co(L)(X2)].CHCl3 (where X = Cl (1), Br (2), or I (3)) is reported, all exhibiting easy-axis magnetic anicotropy. The size of the zero field splitting axial parameter (D) is quantitatively determined (1 = -72; 2 = -67 and 3 = -25 cm-1) using a cantilever torque magnetometry which is further firmly supported by magnetic susceptibility, and EPR measurements. The study of the magnetization relaxation dynamics reveals field-induced slow relaxation of magnetization due to the predominant Raman relaxation process. Theoretical calculations on 1-3 and optimized model complexes of 1 reveal insights into the electronic structure and highlight the impact of steric and electronic effects on modulating the D values. Overall, the studies reported pave the way for designing a new generation of CoII complexes with enhanced axiality and a lower rhombicity.

Impacts of β-diketonate terminal ligands on slow magnetic relaxation and luminescence thermometry in dinuclear DyIII single-molecule magnets.

Lanthanide-based Single-Molecule Magnets (SMMs) with optical and magnetic properties provide a means to understand intrinsic energy levels of 4f ions and their influence on optical and magnetic behaviour. Fundamental understanding of their luminescent and slow relaxation of the magnetization behaviour is critical for targeting and designing SMMs with multiple functionalities. Herein, we seek to investigate the role of DyIII coordination environment and fine electronic structure on the slow magnetic relaxation and luminescence thermometry. Our findings are illustrated through two distinct DyIII complexes, [Dy2(bpm)(hexd)6] (1) and [Dy2(bpm)(hpd)6] (2), (bpm = 2,20-bipyrimidine, hexd = 2,4-hexanedione, hpd = 3,5-heptanedione), by comparing their features with a family of DyIII dinuclear species bridged by bpm. These findings highlight that the hexd- and hpd- ligands exhibit a similar effective barrier to the reversal of magnetization (280-290 K). The values are among the highest for dinuclear DyIII complexes bridged by bpm, due to the low distortion of the DyIII coordination polyhedra and the long Dy-N equatorial bonds. Furthermore, the luminescence performance is affected by the triplet state energy of the terminal ligand, influencing ligand-to-DyIII energy transfer. The hpd- ligand's higher T1 state energy leads to poor ligand-to-DyIII energy transfer, limiting the use of 2 for luminescence thermometry. Conversely, this issue is absent in 1, which offers a relative thermal sensitivity of 0.1 to 0.7% K-1 (10 to 60 K) with a temperature uncertainty below 1 K. These findings contribute to our understanding of lanthanide-based SMMs and facilitate the design of multifunctional materials with tailored magnetic and luminescent properties for molecular electronics and beyond.

Temperature Dependence of Intermolecular Dynamics and Liquid Properties of Deep Eutectic Solvent, Reline.

We investigated the temperature dependence of the intermolecular dynamics, including intermolecular vibrations and collective orientational relaxation, of one of the most typical deep eutectic solvents, reline, using femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES), subpicosecond optical Kerr effect spectroscopy (ps-OKES), and molecular dynamics (MD) simulations. According to fs-RIKES results, the temperature-dependent intermolecular vibrational band peak at ∼90 cm-1 exhibited a redshift with increasing temperature. The density-of-state (DOS) spectrum of reline by MD simulations reproduced this fs-RIKES spectral feature. The decomposition analysis of the DOS spectra showed that all constituent components, including urea, cholinium cation, and chloride anion, also exhibited similar magnitudes of redshifts upon heating, indicating that the three species intermolecularly interact one another. The temperature sensitivity of the intermolecular vibrational frequency was high compared to that of ionic liquids. According to ps-OKES results, the slow orientational relaxation rate increased with increasing temperature; however, this phenomenon was not well explained by the Stokes-Einstein-Debye hydrodynamic model. Analysis of the orientational relaxation time based on the Stokes-Einstein-Debye model indicates that the decoupling between the orientational relaxation time and viscosity occurs at temperatures below ∼330 K. Quantum chemistry calculations of urea and the cholinium cation based on the MP2/6-311++G(d,p) level of theory confirmed that the contribution of intramolecular vibrational bands to low-frequency bands below 200 cm-1 was minimal. The densities, viscosities, electrical conductivities, and surface tensions of reline at various temperatures were also estimated and compared with the dynamics data.

Near-Infrared Magnetic Circularly Polarized Luminescence and Slow Magnetic Relaxation in a Tetrazinyl-Bridged Erbium Metallocene.

The magnetic and magneto-optical properties of a tetrazinyl radical-bridged ErIII metallocene, [(Cp*2ErIII)2(bpytz•-)][BPh4] (1; Cp* = pentamethylcyclopentadienyl, bpytz = 3,6-bis(3,5-dimethyl-pyrazolyl)-1,2,4,5-tetrazine), are reported. As confirmed by these studies strong Ln-rad coupling is achieved, with 1 exhibiting slow magnetic relaxation under a 1000 Oe dc field. The optical and magneto-optical profile of 1 is completed by both near-infrared (NIR) luminescence and magnetic circularly polarized luminescence (MCPL), representing the first example of NIR MCPL with ErIII.

Step-wise assembly of a dysprosium–viologen framework with photoswitchable slow magnetic relaxation under a zero dc field

A dysprosium–viologen framework featuring photoswitchable slow magnetic relaxation under a zero dc field has been constructed step-wise by the incorporation of photochromic layered motifs with the bridging ligand of 2,5-pyrazinedicarboxylate.

Slow magnetic relaxation and strong magnetic coupling in the nitroxyl radical complexes of lanthanide(iii) with diamagnetic ground state (Ln = Lu, Eu).

Radical lanthanide complexes are appealing platforms to investigate the possibility to engineer relevant magnetic couplings between the two magnetic centers by exploiting the strongly donating magnetic orbitals of the radical. In this paper, we report a spectroscopic and magnetic study on [LnRad(NO3)3], where Ln = Eu3+ or Lu3+ and Rad is the tridentate tripodal nitroxyl radical 4,4-dimethyl-2,2-bis(pyridin-2-yl)-1,3-oxazolidine-3-oxyl. A thorough magnetic investigation by Electron Paramagnetic Resonance (EPR) spectroscopy and magnetometry, fully supported by ab initio calculations, allowed us to unravel an unprecedentedly large antiferromagnetic coupling between the Eu3+ and the radical (J 12 = +19.5 cm-1, +J 12 S 1 S 2 convention). Remarkably, both europium and lutetium complexes showed slow magnetization dynamics below 20 K. The field and temperature dependent relaxation dynamics, dominated by Raman and direct processes were modelled simultaneously, allowing us to assess that the Raman process is field dependent.

Impact of paramagnetic CuII and diamagnetic ZnII ions on single-molecule magnetism in heterodinuclear 3d–4f complexes displaying slow relaxation of magnetization

We report the synthesis of heterometallic 3d–4f complexes with paramagnetic CuII and diamagnetic ZnII ions, unveiling rare slow relaxation of magnetization in the Cu–Gd analogue and offering valuable insights into their magnetic dynamics.

Slow Relaxation of the Magnetisation in a Two-Dimensional Metal–Organic Framework with a Layered Square Lattice

Herein, we present the synthesis and structural characterisation of two layered MOFs with the asymmetric ligand 3-chloro,6-cyano-2,5-dihydroxy-1,4-benzoquinone dianion (C6O4(CN)Cl2− = chlorocyananilato). These compounds, formulated as (H3O)[Eu(C6O4(CN)Cl)2(H2O)]·34H2O (1) and (H3O)[Dy(C6O4(CN)Cl)2(H2O)]·44H2O (2), are isostructural and show a (4,4)-layered square structure with the crystallisation water molecules located between the layers. The lanthanoid ions are surrounded by four bis-bidentate chlorocyananilato ligands that connect each LnIII centre with other four, giving rise to square cavities formed by LnIII centres in the vertices and chlorocyananilato ligands as the sides. There is an additional coordinated water molecule that occupies the caped position of the capped square antiprismatic coordination geometry around the LnIII centres. The magnetic properties show the presence of a field-induced slow relaxation of the magnetisation in the DyIII derivative at low temperatures that follows Direct and Orbach relaxation mechanisms with an energy barrier of 36(3) K.

Magnetic Effects in Electrocatalysis Studied with Electrochemical Impedance Spectroscopy: The Cases of Oxygen Reduction and Evolution Reactions on Cobalt Ferrite Electrodes.

Recent years have witnessed an intense effort to unravel magnetic field effects in electrocatalysis, as they can enhance the performance of common electrocatalysts. Both experimental and theoretical studies have shown that magnetic fields may affect, among others, the macroscopic spin-orbital ordering, charge transport, bubble release, and electron transfer kinetics. This paper highlights Electrochemical Impedance Spectroscopy (EIS) as a tool to analyze and separate the effects of magnetic field on both the oxygen reduction and evolution reactions at cobalt iron oxide electrodes. The unequivocal existence of magnetic field effects is demonstrated through EIS, which provides additional information useful to individuate the magnetic field effects. In the almost superparamagnetic nanoparticles studied here, while the magnetic field impact is positive for oxygen reduction, it turns out to be negligible in the case of oxygen evolution. In addition, this study reveals new significant insights, including the exceptionally slow relaxation kinetics of the magnetic effects and the significance of magnetic-induced surface modifications. The fact that the effects virtually disappear in the presence of electrolyte cesium ions points to the key role of electrode surface states. This study showcases the potential of EIS to probe the effects of permanent magnetic fields in electrocatalysis.

Predicting Magnetic Barriers in Lanthanide Complexes with Electrostatic Potential Charges.

Single-molecule magnets (SMMs) with slow relaxation of magnetization and blocking temperatures above that of liquid nitrogen are essential for practical applications in high-density data storage devices and quantum computers. A rapid and accurate prediction of the effective magnetic relaxation barrier (Ueff) is needed to accelerate the discovery of high-performance SMMs. Using density functional theory and multireference calculations, we explored correlations between Ueff, partial atomic charges, and the anisotropic barrier for a series of sandwich-type lanthanide complexes containing cyclooctatetraene, substituted cyclopentadiene, phospholyl, boratabenzene, or borane ligands. Our results show a correlation between the electrostatic potential charge of the lanthanide ion in the complex and Ueff. Systematic ligand modifications show that reducing ligand nucleophilicity and incorporating soft bases enhance magnetic anisotropy and Ueff values. This work identifies a correlation to predict Ueff values and optimization of ligand coordination environments in lanthanide-based SMMs.

Absolute and Relative Binding Free Energy Calculations of Nucleotides to Multiple Protein Classes.

Polyphosphate nucleotides, such as ATP, ADP, GTP, and GDP, play a crucial role in modulating protein functions through binding and/or catalytically activating proteins (enzymes). However, accurately calculating the binding free energies for these charged and flexible ligands poses challenges due to slow conformational relaxation and the limitations of force fields. In this study, we examine the accuracy and reliability of alchemical free energy simulations with fixed-charge force fields for the binding of four nucleotides to nine proteins of various classes, including kinases, ATPases, and GTPases. Our results indicate that the alchemical simulations effectively reproduce experimental binding free energies for all proteins that do not undergo significant conformational changes between their triphosphate nucleotide-bound and diphosphate nucleotide-bound states, with 87.5% (7 out of 8) of the absolute binding free energy results for 4 proteins within ±2 kcal/mol of experimental values and 88.9% (8 out of 9) of the relative binding free energy results for 9 proteins within ±3 kcal/mol of experimental values. However, our calculations show significant inaccuracies when divalent ions are included, suggesting that nonpolarizable force fields may not accurately capture interactions involving these ions. Additionally, the presence of highly charged and flexible ligands necessitates extensive conformational sampling to account for the long relaxation times associated with long-range electrostatic interactions. The simulation strategy presented here, along with its demonstrated accuracy across multiple protein classes, will be valuable for predicting the binding of nucleotides or their analogs to protein targets.

Does the unusual phenomenon of sustained force circumvent the speed-endurance trade off in the jaw muscle of the southern alligator lizard (Elgaria multicarinata)?

The jaw muscles of the southern alligator lizard, Elgaria multicarinata, are used in prolonged mate-holding behavior, and also to catch fast prey. In both males and females, these muscles exhibit an unusual type of high endurance known as sustained force in which contractile force does not return to baseline between subsequent contractions. This phenomenon is assumed to facilitate the prolonged mate-holding observed in this species. Skeletal muscle is often subject to a speed-endurance trade off. Here we determine the isometric twitch, tetanic, and isotonic force-velocity properties of the jaw muscles at ∼24°C as metrics of contractile speed and compare these properties to a more typical thigh locomotory muscle, to determine whether endurance by sustained force allows for circumvention of the speed-endurance trade-off. The specialized jaw muscle is generally slower than the more typical thigh muscle; time to peak twitch force, twitch 90% relaxation time (p<0.01), and tetanic 90% and 50% relaxation times (p<0.001) are significantly longer, and force-velocity properties are significantly slower (p<0.001), in the jaw than the thigh muscle. However, there seem to be greater effects on relaxation rates and shortening velocity that on force rise times; there was no effect of muscle on time to peak, or 50% of tetanic force. Hence, the jaw muscle of the southern alligator lizard does not seem to circumvent the speed-endurance trade-off. However, the maintenance of force rise times despite slow relaxation, potentially enabled by the presence of hybrid fibers, may allow this muscle to meet the functional demand of prey capture.

Calixarene-like Lanthanide Single-Ion Magnets Based on NdIII, GdIII, TbIII and DyIII Oxamato Complexes

In this work, we describe the synthesis, crystal structures and magnetic properties of four air-stable mononuclear lanthanide(III) complexes with the N-(2,4,6-trimethylphenyl)oxamate (Htmpa) of formula: n-Bu4N[Nd(Htmpa)4(H2O)]·4H2O (1), n-Bu4N[Gd(Htmpa)4(H2O)]·3DMSO·2H2O (2), n-Bu4N[Tb(Htmpa)4(H2O)]·3DMSO·1H2O (3) and n-Bu4N[Dy(Htmpa)4(H2O)]·3DMSO·2H2O (4) (n-Bu4N+ = n-tetrabutylammonium; DMSO = dimethylsulfoxide). Their crystal structures reveal the occurrence of calixarene-type monoanionic species containing all-cis-disposed Htmpa ligands and one water molecule coordinated with the respective LnIII ion (Ln = Nd, Gd, Tb and Dy), featuring a nine-coordinated environment with muffin (MFF-9) (1) or spherical-capped square antiprism (CSAPR-9) (2–4) geometry. The major difference between their crystal structures is related to the nature of crystallization solvent molecules, either water (1) or both DMSO and water (2–4). The intermolecular hydrogen bonds among the self-complementary Htmpa ligands in all four compounds mediated a 2 D supramolecular network in the solid state. Direct-current (dc) magnetic properties for 1–4 show typical behavior for the ground state terms of the LnIII ions [4I9/2 (Nd); 8S7/2(Gd), 7F6 (Tb), 6H15/2 (Dy)]. Alternating-current (ac) magnetic measurements reveal the presence of slow magnetic relaxation without the presence of a dc field only for 4. In contrast, field-induced slow magnetic relaxation behavior was found in complexes 1, 2 and 3.

Engineering Mononuclear Ln(III) Complexes with a Pseudo-Macrocyclic Hexadentate N4O2 Schiff Base Ligand Exhibiting Slow Magnetic Relaxation

Engineering Mononuclear Ln(III) Complexes with a Pseudo-Macrocyclic Hexadentate N4O2 Schiff Base Ligand Exhibiting Slow Magnetic Relaxation

Diamagnetic Carrier-Doping-Induced Continuous Electronic and Magnetic Crossover in One-Dimensional Coordination Polymers.

The potential to introduce tunable electrical conductivity and molecular magnetism through carrier doping in metal-organic coordination polymers is particularly promising for nanoelectronics applications. Precise control of the doping level is essential for determining the electronic and magnetic properties. In this study, we present a series of one-dimensional coordination polymers, {(HNEt3)0.5[CuxCo(1-x)(L)]}n (HNEt3 = triethylammonium, L = 1,2,4,5-tetrakis(methanesulfonamido)benzene), doped with diamagnetic Cu1+ carriers. Through comprehensive characterization of the structural, optical, and magnetic properties, we observed continuous electronic and magnetic crossover as the doping level was gradually increased. When x < 0.5, the doped compounds exhibit ferromagnetic insulating behavior with very high energy barriers (Ueff up to 560 K) and excellent slow relaxation of magnetization. At x = 0.5, {(HNEt3)0.5[Cu0.5Co0.5(L)]}n functions as a paramagnetic semiconductor at high temperatures and a single-molecule magnet at low temperatures. When x > 0.5, the doped compounds act as diluted antiferromagnetic semiconductors with narrow band gaps (Ea = 0.2 eV). The emergence of such rich electronic and magnetic crossovers is ascribed to the cooperation of the strong electron-donating ability of the ligand and the pronounced crystal-field effects. Our findings indicate that one-dimensional (1D) coordination polymers are promising for the design of novel low-dimensional magnetic semiconductors.

THz‐EPR‐Based Direct Spectroscopic Determination of the Anisotropy Barrier of a Heteroleptic Bis‐Chelate Cobalt(II) Complex with Bis(sulfonamido)benzene Ligand and its Dynamic Magnetic Properties

AbstractA new mononuclear, four‐coordinate heteroleptic cobalt(II) complex 1 was synthesised utilising N,N′‐1,2‐Phenylenebis‐(4‐methylbenzenesulfonamide) and 6,6′‐Dimethyl‐2,2′‐bipyridine as ligands and structurally characterised. Magnetic susceptibility and magnetisation measurements, along with ab initio calculations, revealed a large easy‐axis type magnetic anisotropy of the cobalt(II) centre. Frequency‐dependent ac susceptibility measurements revealed out‐of‐phase signals, indicating a slow relaxation of magnetisation, even in the absence of an additional static magnetic field. The corresponding relaxation behaviour can be attributed to a combination of Orbach and phonon‐assisted processes within the observable temperature range. Using FD‐FT THz‐EPR spectroscopy, the magnetic anisotropy barrier was determined to be unexpectedly large with a value of 146.4 . The deviation from the expected barrier, based on correlations with the elongation parameter , is attributed to the charge distribution in the coordination environment.

Synthesis, Structure, and Properties of 2D Lanthanide(III) Coordination Polymers Constructed from Cyclotriphosphazene-Functionlized Hexacarboxylate Ligand.

The design and synthesis of novel lanthanide-based coordination polymers (Ln-CPs) from flexible organic ligands is still attractive and challenging. In this work, two isostructural Ln-CPs with a unique 2D network, namely, [Ln2(H3L)2(DMF)]]n (Ln = Dy for 1, Tb for 2) based on a flexible polycarboxylic acid ligand hexakis(4-carboxylato-phenoxy)cyclotriphosphazene (H6L), have been solvothermally synthesized and structurally characterized. Significantly, it is the first observation of polycarboxylic acid ligands participating in coordination in the construction of coordination polymers in the form of semi-deprotonation. Magnetic measurements showed the presence of field-induced slow magnetic relaxation in complex 1. The luminescence property of 2 had been studied in the solid state at room temperature.