Quantum Tunneling Of Magnetization Research Articles

Low-Energy Magnetic States of Tb Adatom on Graphene.

Electronic structure and magnetic interactions of a Tb adatom on graphene are investigated from first principles using combination of density functional theory and multiconfigurational quantum chemistry techniques including spin-orbit coupling. We determine that the six-fold symmetry hollow site is the preferred adsorption site and we investigate electronic spectrum for different adatom oxidation states including Tb3+, Tb2+,Tb1+, and Tb0. For all charge states, the Tb 4f8configuration is retained with other adatom valence electrons being distributed over 5dxy, 5dx2+y2, and 6s/5d0single-electron orbitals. We find strong intra-site adatom exchange coupling that ensures that the 5d6sspins are parallel to the 4fspin. For Tb3+, the energy levels can be described by theJ= 6 multiplet split by the graphene crystal field. For other oxidation states, the interaction of 4felectrons with spin and orbital degrees of freedom of 6s5delectrons in the presence of spin-orbit coupling results in the low-energy spectrum composed closely lying effective multiplets that are split by the graphene crystal field. Stable magnetic moment is predicted for Tb3+and Tb2+adatoms due to uniaxial magnetic anisotropy and effective anisotropy barrier around 440 cm-1controlled by the temperature assisted quantum tunneling of magnetization through the third excited doublet. On the other hand, in-plane magnetic anisotropy is found for Tb1+and Tb0adatoms. Our results indicate that the occupation of the 6s5dorbitals can dramatically affect the magnetic anisotropy and magnetic moment stability of rare earth adatoms.

Effect of Substituents in Equatorial Hexaazamacrocyclic Schiff Base Ligands on the Construction and Magnetism of Pseudo D6h Single-Ion Magnets.

Three mononuclear DyIII compounds [DyL1(Ph3SiO)2][BPh4]·MeCN·2H2O (1), [DyL2(Ph3SiO)2][BPh4]·C2H5OH·H2O (2), and [DyL3(Ph3SiO)(OAc)][BPh4]·CH3OH·3H2O (3) and their corresponding YIII diluted analogues [Dy0.0967Y0.9033L1(Ph3SiO)2][BPh4]·MeCN·2H2O (1@Y), [Dy0.2668Y0.7332L2(Ph3SiO)2][BPh4]·C2H5OH·H2O (2@Y), and [Dy0.1260Y0.8740L3(Ph3SiO)(OAc)][BPh4]·CH3OH·3H2O (3@Y) were synthesized with hexaazamacrocyclic Schiff base ligands as an equatorial ligand. The substituents in the equatorial hexaazamacrocyclic Schiff base ligand show a significant effect on the replacement of the axial ligands. Compounds 1, 2, and 3 are typical zero dc field single-molecule magnets with effective energy barriers (Ueff) of 1092(6), 946.1(7), and 150.1(9) K, respectively. Although the effective energy barriers of 1 and 2 are close, the magnetic hysteresis remains open up to 20 K for 1, twice as large as that of 2 (10 K), which is different from the previously reported compounds, probably due to nonplanarity N6 in the equator. Ab initio calculations indicate that the ground states of compounds 1 and 2 exhibit high anisotropy and pure second and third excited states, while compound 3 exhibits pure ground-state anisotropy and highly mixed excited states, leading to the easy occurrence of quantum tunneling of magnetization between the ground and excited states in compound 3. This work indicates that the substituents in equatorial hexaazamacrocyclic Schiff base ligands have a significant effect on the construction and magnetic properties of DyIII SIMs with D6h symmetry.

Long-Lived Magnetization in an Atomic Spin Chain Tuned to a Diabolic Point.

Scaling magnets down to where quantum size effects become prominent triggers quantum tunneling of magnetization (QTM), profoundly influencing magnetization dynamics. Measuring magnetization switching in an Fe atomic chain under a carefully tuned transverse magnetic field, we observe a nonmonotonic variation of magnetization lifetimes around a level crossing, known as the diabolic point (DP). Near DPs, local environment effects causing QTM are efficiently suppressed, enhancing lifetimes by three orders of magnitude. Adjusting interatomic interactions further facilitates multiple DPs. Our Letter provides a deeper understanding of quantum dynamics near DPs and enhances our ability to engineer a quantum magnet.

Exchange-biased quantum tunneling of magnetization in a nanomagnetic dimer via a Josephson current

We investigate a Josephson junction where the weak link consists of a nanomagnetic dimer, featuring two large, antiferromagnetically coupled spins under simple easy-axis anisotropy. In this setup, the exchange coupling constant serves as a transverse anisotropy constant, and the quantum tunneling of the magnetization is influenced by the supercurrent, which behaves like an external magnetic field applied along the hard axis. Our results demonstrate that the superconducting current induces non-Kramers freezing and unfreezing of the magnetic moment’s tunneling within a biaxial spin model driven by exchange interaction. We derive an exact expression for the quenching condition caused by the exchange coupling. Additionally, we extend our analysis to tunneling phenomena in two antiferromagnetically or ferromagnetically coupled spins biased by the anisotropic exchange interaction, revealing more varied cases of tunnel splitting.

Enhancement of Effective Energy Barrier and Magnetic Blocking Temperature in Tetraoxolene Radical Coupled Dinuclear Dysprosium Complex.

A well-judged combination of a high axial ligand field and a bridging radical ligand in a dinuclear lanthanide complex provides a single-molecule magnet with a higher effective energy barrier for magnetic relaxation and blocking temperature compared to its non-radical analog due to significant magnetic exchange coupling between radical and Ln(III) ions. In this work, we report two chloranilate (CA) bridged dinuclear dysprosium complexes, [{(bbpen)Dy(μ2-CA)Dy(bbpen)}] (1Dy) and [{(bbpen)Dy(μ2-CA•)Dy(bbpen)}-{CoCp2}+] (2Dy), where 2Dy is the radical bridged Dy-complex obtained via the chemical reduction of bridging CA moiety (H2bbpen = N,N'-bis(2-hydroxybenzyl)-N,N'-bis(2-methylpyridyl)ethylenediamine). The presence of high electronegative phenoxide moiety enhances the axial anisotropy of pseudo-square antiprismatic Dy(III) ions. The diffused spin of radical is efficiently coupled with anisotropic Dy(III) centres and decreases the quantum tunnelling of magnetization (QTM) in the magnetic relaxation process. The magnetic relaxation of 1Dy follows Orbach, Raman, and QTM processes whereas for 2Dy it follows Orbach and Raman Processes. Due to less involvement of the QTM relaxation process, 2Dy shows a higher thermal energy barrier (Ueff = 700 K) and a high blocking temperature (6.7 K), compared to its non-radical analog. Remarkably, the radical coupled 2Dy complex shows the highest energy barrier among the radical bridged Dy(III)-based SMMs to date.

Synergy of Experiment and Broadened Exploration of Ab Initio Calculations for Understanding of Lanthanide-Pentacyanidocobaltate Molecular Nanomagnets and Their Optical Properties.

We present a synergistic experimental-theoretical methodology for the investigation of lanthanide-based single-molecule magnets (SMMs), demonstrated using the example of novel heterometallic molecules incorporating Nd3+/Ce3+ ions combined with three different, rarely explored, pentacyanidocobaltate(III) metalloligands, [CoIII(CN)5(azido/nitrito-N/iodido)]3-. The theoretical part of our approach broadens the exploration of ab initio calculations for lanthanide(III) complexes toward the convenient simulations of such physical characteristics as directional dependences of Helmholtz energy, magnetization, susceptibility, and their thermal and field evolution, as well as light absorption and emission bands. This work was conducted using newly designed SlothPy software (https://slothpy.org). It is introduced as an open-source Python library for simulating various physical properties from first-principles based on results of electronic structure calculations obtained within popular quantum chemistry packages. The computational results were confronted with spectroscopic and ac/dc-magnetic data, the latter analyzed using previously designed relACs software. The combination of experimental and computational methods gave insight into phonon-assisted magnetic relaxation mechanisms, disentangling them from the temperature-independent quantum tunneling of magnetization and emphasizing the role of local-mode processes. This study provides an understanding of the changes in lanthanide(III) magnetic anisotropy introduced with pentacyanidocobaltates(III) modifications, theoretically exploring also potential applications of reported compounds as anisotropy switches or optical thermometers.

Field-induced slow magnetic relaxation in a mononuclear Dy(III) complex with octahedral geometry

We have synthesized a mononuclear Dy(III)-based complex, [Dy(CyPh2PO)3Cl3)] (1) (CyPh2PO = cyclohexylbisphenylphosphine oxide), constructed from a phosphine oxide ligand and a light halogen Cl donor. The Dy(III) ion presents an octahedral geometry where two O atoms from two phosphine ligands locate at two vertexes, while the equatorial positions are completed by three Cl anions and a O atom from another phosphine ligand. Magnetism results reveal that slow relaxation of the magnetizations exists in 1 under an extra dc field because of the significant quantum tunnelling of magnetization (QTM) at 0 Oe dc field. The lighter Cl ions in equatorial plane result in a larger effect to QTM, and thus smaller contribution to slow magnetic relaxation.

Structures and Single-Molecule Magnet Behavior of Dy3 and Dy4 Clusters Constructed by Different Dysprosium(III) Salts.

Using the Schiff base ligand H2L-pyra (N'-(2-hydroxybenzoyl)pyrazine-2-carbohydrazonamide) with multiple dentate sites, the trinuclear DyIII-based complex [Dy3(HL-pyra)2(L-pyra)2(CH3COO)3]·2H2O (1) was synthesized. By analyzing the fragmented assembly process and fine-tuning the bridging anions, complex [Dy4(HL-pyra)2(L-pyra)4(NO3)2(H2O)2]·8H2O (2) with different nuclear numbers was successfully synthesized. Magnetic studies demonstrated that 1 did not exhibit magnetic relaxation behavior under the external field; however, 2 exhibited zero-field single-molecule magnetic relaxation behavior with an effective energy barrier (Ueff) of 197.44 K. This is attributed to the improved anisotropy of the single ion after the normalization of the crystal structure, thus realizing the molecular magnetic switching. Moreover, magnetic dilution analysis of 2 demonstrated that the weak magnetic interaction between metal ions inhibited the occurrence of quantum tunneling of magnetization (QTM), resulting in high-performance single-molecule magnet (SMM) behavior. The reasons for the magnetic difference between these two complexes were analyzed using ab initio calculation and magneto-structural correlations. This study provides a reasonable prediction of the ideal configuration of the approximately parallelogram DyIII-based SMMs, thus offering an effective approach for synthesizing Dy4 complexes with excellent properties.

Auxiliary Rather Than Dominant. The Role of Direct Dy-S Coordination in Single-Molecule Magnet Unveiled via ab initio Study.

The role of Dy-S coordination in a single-molecule magnet (SMM) is investigated via an ab initio study in a group of mononuclear structures. The SMM performance of this group is well interpreted via a concise criterion consisting of long quantum tunneling of magnetization (QTM) time τQTM and high effective barrier for magnetic reversal Ueff. The best SMMs in the selected group, i.e., 1Dy (CCDC refcode: PUKFAF) and 2Dy (CCDC refcode: NIKSEJ), are just those holding the longest τQTM and the highest Ueff simultaneously. Further analysis based on the crystal field model and ab initio magneto-structural exploration indicates that the influence of Dy-S coordination on the SMM performance of 1Dy is weaker than that of axial Dy-O coordination. Thus, Dy-S coordination is more likely to play an auxiliary role rather than a dominant one. However, if placed at the suitable equatorial position, Dy-S coordination could provide important support for good SMM performance. Consequently, starting from 1Dy, we built two new structures where Dy-S coordination only exists at the equatorial position and two axial positions are occupied by strong Dy-O/Dy-F coordination. Compared to 1Dy and 2Dy, these new ones are predicted to have significantly longer τQTM and higher Ueff, as well as a nearly doubled blocking temperature TB. Thus, they are probable candidates of SMM having clearly improved performance.

Short Didysprosium Covalent Bond Enables High Magnetization Blocking Temperature of a Direct 4f-4f Coupled Dinuclear Single-Molecule Magnet.

Coupling two magnetic anisotropic lanthanide ions via a direct covalent bond is an effective way to realize high magnetization blocking temperature of single-molecule magnets (SMMs) by suppressing quantum tunneling of magnetization (QTM), whereas so far only single-electron lanthanide-lanthanide bonds with relatively large bond distances are stabilized in which coupling between lanthanide and the single electron dominates over weak direct 4f-4f coupling. Herein, we report for the first time synthesis of short Dy(II)-Dy(II) single bond (3.61 Å) confined inside a carbon cage in the form of an endohedral metallofullerene Dy2@C82. Such a direct Dy(II)-Dy(II) covalent bond renders a strong Dy-Dy antiferromagnetic coupling that effectively quenches QTM at zero magnetic field, thus opening up magnetic hysteresis up to 25 K using a field sweep rate of 25 Oe/s, concomitant with a high 100 s magnetization blocking temperature (TB,100s) of 27.2 K.

Cobalt(II) Single-Ion Magnet Coordinated by Double Deprotonation of 2,2'-Bipyridine-6,6'-diol Ligands.

In this study, we synthesized a new Co(II) complex, [NMe4]2[Co(bpyO2)2] (1), using deprotonated 2,2'-bipyridine-6,6'-diol ligands (bpyO2 2-). This compound exhibits a significant zero-field splitting (D) value. The far-infrared magneto spectroscopy and high-frequency and field electron paramagnetic resonance (HFEPR) measurements indicated that compound 1 possesses D = -54.8 cm-1 and E ∼ 0 cm-1. These findings were subsequently confirmed by other experimental data, including DC magnetic susceptibilities and variable temperature and variable magnetic field reduced magnetizations. Additionally, we conducted a series of AC magnetic susceptibility measurements to investigate the kinetics of magnetization relaxation. Below 6.6 K and under zero external magnetic field, fast quantum tunneling of magnetization (QTM) dominates (∼570 Hz), and temperature-independent out-of-phase signals are observed. Above 8.1 K, temperature-dependent behavior is observed. Furthermore, we examined the AC magnetic susceptibility behavior under external magnetic fields ranging from 300 to 4000 G. The effect of QTM is significantly reduced in the presence of an external magnetic field. Temperature-dependent behavior is primarily governed by Raman relaxation. Through structural analysis of compound 1 and a series of pure nitrogen-coordinated single-ion magnets (SIMs), we propose that the oxo substituents from the double-deprotonated form of the 2,2'-bipyridine-6,6'-diol ligands donate their negative charge to the pyridine ring, forming amido anion sites. This triggers a more pronounced out-of-phase signal than that observed in pure pyridine-coordinated compounds. Moreover, we observed intermolecular interactions, including intermolecular hydrogen bonding, which, to some extent, influenced the slow relaxation of molecules. Therefore, we speculate that the slow relaxation phenomenon of compound 1 may be attributed to the combination of oxo back-donating effects and intermolecular interactions.

Field-induced slow magnetic relaxation in a distorted trigonal prismatic cobalt(II) complex

Two mononuclear complexes [M(DQ)(OTf)](OTf)·H2O (M = Co for 1 and Fe for 2, DQ = 6,6′′-di(quinolin-8-yl)-4′-phenyl-2,2′:6′,2′′-terpyridine) with distorted trigonal prismatic geometry have been synthesized and characterized. Crystal structures show that the 3d ions are helically coordinated by a pentadentate DQ and encapsulated by a terminal OTf− anion, resulting in [MN5O] coordination environments. Magnetic measurements and ab initio calculation indicate that complex 1 displays easy axis anisotropy and exhibits field-induced slow magnetic relaxation which is dominated by Raman and direct processes. For 2, no slow magnetic relaxation had been recorded owing to the significant fast quantum tunneling of magnetization.

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 at 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.

Magnetic Anisotropy and Relaxation in Four-Coordinate Cobalt(II) Single-Ion Magnets with a [CoIIO4] Core.

A mononuclear four-coordinate Co(II) complex with a [CoIIO4] core, namely, PPN[Li(MeOH)4][Co(L)2] (1) (PPN = bis(phosphoranediyl)iminium; H2L = perfluoropinacol), has been studied by X-ray crystallography, magnetic characterization, and theoretical calculations. This complex presents a severely distorted coordination geometry. The O-Co-O bite angle is 83.42°/83.65°, and the dihedral twist angle between the O-Co-O chelate planes is 55.6°. The structural distortion results in a large easy-axis magnetic anisotropy with D = -104(1) cm-1 and a transverse component with |E| = +4(2) cm-1. Alternating current (ac) susceptibility measurements demonstrate that 1 exhibits slow relaxation of magnetization at zero static field. However, the frequency-dependent out-of-phase (χ"M) susceptibilities of 1 at 0 Oe do not show a characteristic maximum. Upon the application of a dc field or the dilution with a diamagnetic Zn matrix, the quantum tunneling of magnetization (QTM) process can be successfully suppressed. Notably, after dilution with the Zn matrix, the obtained sample exhibits a structure different from that of the pristine complex. In this altered sample, the asymmetric unit does not contain the Li(MeOH)4+ cation, resulting in an O-Co-O bite angle of 86.05° and a dihedral twist angle of 75.84°, thereby leading to an approximate D2d symmetry. Although such differences are not desirable for magnetic studies, this study still gives some insights. Theoretical calculations reveal that the D parameter is governed by the O-Co-O bite angle, in line with our previous report for other tetrahedral Co(II) complex with a [CoIIN4] core. On the other hand, the rhombic component is found to increase as the dihedral angle deviates from 90°. These findings provide valuable guidelines for fine-tuning the magnetic properties of Co(II) complexes.

Tailoring single-ion magnet properties of coordination polymer C11H18DyN3O9 (Dy-CP) using the radial effective charge model (RECM) and superposition model (SPM).

We investigate Dy-based coordination polymer C11H18DyN3O9 (Dy-CP) exhibiting single-ion magnet (SIM) properties, e.g., quantum tunnelling of magnetization (QTM), magnetic anisotropy, magnetic relaxation, and effective energy barrier (Ueff). To elucidate the underlying mechanisms, crystal field parameters (CFPs) for Dy3+ ions were modelled using the radial effective charge model (RECM) and superposition model (SPM), and the computational packages SIMPRE and SPECTRE. The modelled CFPs enable the prediction of the energy levels and associated wave functions, which successfully explain the field-induced Dy-CP SIM properties. The so-calculated magnetic susceptibility and isothermal magnetization match the experimental data reasonably well. The smaller energy separations of the first (Δ0-1 ∼ 31 cm-1) and the second (Δ0-2 = 74 cm-1) excited Kramers doublets suggest small Ueff = 65 cm-1 for Dy-CP. The magnetic moments of Dy3+ ions exhibit an easy-axis type magnetic anisotropy in the ground state, but change orientation in the excited states due to mixing of states from different Kramers doublets. Low-symmetry CF components play a crucial role in connecting different |±MJ〉 states within the ground multiplet, resulting in QTM and magnetic relaxation to the ground state occurring via the excited states. The RECM and SPM calculated CFP sets are standardized employing the 3DD package to enable meaningful comparison and assessing their mutual equivalence. The results demonstrate the correlation between structural and electronic features of the molecule and site symmetry and distortion of the local coordination polyhedra with SIM properties, offering insights for rational design of new SIMs. The importance of considering low-symmetry aspects in CFP modelling for accurate predictions of magnetic properties is highlighted. This study provides deeper understanding of field-induced behaviour in rare-earth-based SIMs and approaches for rationalization of experimentally measured SIMs' properties.

Coordination-driven assembly of dysprosium layers into a framework featuring enhanced energy barriers and quantum tunneling of magnetization

An orchestrated reaction of Dy(ClO4)3·6H2O with the organic ligand of N′-(2-hydroxybenzylidene)pyrazine-N-oxide-carbohydrazide (H2L) affords a layered building block, denoted as {[Dy(L)(H2O)(CH3OH)]ClO4·2CH3OH}n (1).

Substituted fullerenes as a promising capping ligand towards stabilization of exohedral Dy(III) based single-ion magnets: a theoretical study.

Organometallic dysprosocenium-based molecular magnets are the forefront runners in offering giant magnetic anisotropy and blocking temperatures close to the boiling point of liquid nitrogen. Attaining linearity in the organometallic dysprosocenium complexes is the key to generating giant magnetic anisotropy and blocking barriers. In the present study, we have unravelled the coordination ability of the substituted fullerene (C55X5)- (where X = CCH3, B, and N) generated by fencing around the five-membered ring of fullerene towards stabilizing a new family of exohedral dysprosium organometallic complexes showcasing giant magnetic anisotropy and blockade barriers. Eight exohedral mononuclear dysprosium organometallic complexes, namely [Dy(η5-C55X5)(η4-C4H4)] (1), [Dy(η5-C55X5)(η5-Cp)]+ (2), [Dy(η5-C55X5)(η5-Cp*)]+ (3), [Dy(η5-C55X5)(η6-C6H6)]2+ (4), [Dy(η5-C55X5)(η8-C8H8)] (5), [Dy(η5-C55X5)2]+ (6) (where X = CCH3), [Dy(η5-C55B5)2]+ (7) and [Dy(η5-C55N5)2]+ (8), were studied using scalar relativistic density functional theory (SR-DFT) and the complete active space self-consistent field (CASSCF) methodology to shed light on the structure, stability, bonding and single-ion magnetic properties. SR-DFT calculations predict complexes 1-8 to be highly stable, with a strictly linear geometry around the Dy(III) ion in complexes 6-8. Energy Decomposition Analysis (EDA) predicts the following order for interaction energy (ΔEint value): 5 > 1 > 2 ≈ 3 > 6 > 7 > 8 > 4, with sizable 4f-ligand covalency in all the complexes. CASSCF calculations on complexes 1-8 predict stabilization of mJ |±15/2〉 as the ground state for all the complexes except for 5, with the following trend in the Ucal values: 6 (1573 cm-1) ≈ 3 (1569 cm-1) > 1 (1538 cm-1) > 8 (1347 cm-1) > 2 (1305 cm-1) > 7 (1284 cm-1) > 4 (1125 cm-1) > 5 (108 cm-1). Ab initio ligand field theory (AILFT) analysis provides a rationale for Ucal ordering, where π-type 4f-ligand interactions in complexes 1-4 and 6-8 offer giant barrier height while the large (C8H8)2- rings generate δ-type interaction in 5, which diminishes the axiality in the ligand field. Our detailed finding suggests that the exohedral organometallic dysprosocenium complexes are more linear compared to bent [DyCp*2]+ cations and display a giant barrier height exceeding 1500 cm-1 with negligible quantum tunnelling of magnetization (QTM) - a new approach to design highly anisotropic dysprosium organometallic complexes.

Theoretical exploration of single-molecule magnetic and single-molecule toroic behaviors in peroxide-bridged double-triangular {MII3LnIII3} (M = Ni, Cu and Zn; Ln = Gd, Tb and Dy) complexes.

Detailed state-of-the-art ab initio and density functional theory (DFT) calculations have been undertaken to understand both Single-Molecule Magnetic (SMM) and Single-Molecule Toroic (SMT) behaviors of fascinating 3d-4f {M3Ln3} triangular complexes having the molecular formula [MII3LnIII3(O2)L3(PyCO2)3](OH)2(ClO4)2·8H2O (with M = Zn; Ln = Dy (1), Tb (2) & Gd (3) and M = Cu; Ln = Dy (4), Tb (5) & Gd (6)) and [Ni3Ln3(H2O)3(mpko)9(O2)(NO3)3](ClO4)·3CH3OH·3CH3CN (Ln = Dy (7), Tb (8), and Gd (9)) [mpkoH = 1-(pyrazin-2-yl)ethanone oxime]. All these complexes possess a peroxide ligand that bridges the {LnIII3} triangle in a μ3-η3:η3 fashion and the oxygen atoms/oxime of co-ligands that connect each MII ion to the {LnIII3} triangle. Through our computational studies, we tried to find the key role of the peroxide bridge and how it affects the SMM and SMT behavior of these complexes. Primarily, ab initio Complete Active Space Self-Consistent Field (CASSCF) SINGLE_ANISO + RASSI-SO + POLY_ANISO calculations were performed on 1, 2, 4, 5, 7, and 8 to study the anisotropic behavior of each Ln(III) ion, to derive the magnetic relaxation mechanism and to calculate the LnIII-LnIII and CuII/NiII-LnIII magnetic coupling constants. DFT calculations were also performed to validate these exchange interactions (J) by computing the GdIII-GdIII and CuII/NiII-GdIII interactions in 3, 6, and 9. Our calculations explained the experimental magnetic relaxation processes and the magnetic exchange interactions for all the complexes, which also strongly imply that the peroxide bridge plays a role in the SMM behavior observed in these systems. On the other hand, this peroxide bridge does not support the SMT behavior. To investigate the effect of bridging ions in {M3Ln3} systems, we modeled a {ZnII3DyIII3} complex (1a) with a hydroxide ion replacing the bridged peroxide ion in complex 1 and considered a hydroxide-bridged {CoIII3DyIII3} complex (10) having the formula [Co3Dy3(OH)4(OOCCMe3)6(teaH)3(H2O)3](NO3)2·H2O. We discovered that as compared to the LoProp charges of the peroxide ion, the greater negative charges on the bridging hydroxide ion reduce quantum tunneling of magnetization (QTM) effects, enabling more desirable SMM characteristics and also leading to good SMT behavior.

Modulation of the magnetic properties of mononuclear Dy(III) complexes by tuning the coordination geometry and local symmetry.

Precise control of the crystal field and local symmetry around the paramagnetic spin center is crucial for the design and synthesis of single-molecule magnets (SMMs). Herein, three mononuclear Dy(III)-based complexes, [Dy(LN6)(CH3COO)2](BPh4)(CH2Cl2) (1), [Dy(LN6)(2,6-Cl-4-NO2-PhO)(H2O)2]2(PF6)2(H2O)(2,6-Cl-4-NO2-PhO)2 (2) and [Dy(LN6)(2,6-Cl-4-NO2-PhO)2](BPh4)(CH2Cl2)2 (3) (LN6 = N6-hexagonal plane accomplished by a neutral Schiff base ligand formed from 2,6-diacetylpyridine and ethylenediamine), are successfully isolated. In these complexes, the Dy(III) centers are coordinated with six neutral N atoms from a nonrigid equatorial ligand, while different oxygen-bearing ligands are arranged at the axial positions of the central ions by gradual regularization of the axial ligands. As a result, Dy(III) ions in the three complexes exhibit various coordination geometries, forming a ten-coordinate tetradecahedron for 1, a nine-coordinate muffin configuration for 2 and a distorted eight-coordinate hexagonal bipyramid for 3. Magnetic studies reveal that all complexes exhibit no SIM behaviour under zero dc field, due to the predominant quantum tunneling of magnetization (QTM), which can be effectively suppressed by additional dc fields. Experiments, coupled with theoretical calculations, demonstrate that varying local symmetries and coordination geometries are synergistically responsible for the disparities of QTM and uniaxial anisotropy, resulting in notably different magnetic properties.

Constructing high axiality mononuclear dysprosium molecular magnets via a regulation-of-co-ligands strategy.

Two lanthanide complexes with formulae [DyIII(LN5)(pentafluoro-PhO)3] (1) and [DyIII(LN5)(2,6-difluoro-PhO)2](BPh4) (2) (LN5 = 2,14-dimethyl-3,6,10,13,19-pentaazabicyclo[13.3.1]nonadecal (19),2,13,15,17-pentaene) were structurally and magnetically characterized. DyIII ions lie in the cavity of a five coordinate nitrogen macrocycle, and in combination with the introduction of multi-fluorinated monodentate phenoxyl coligands a high axiality coordination symmetry is built. Using the pentafluorophenol co-ligand, complex 1 with a D2d coordination environment, is obtained and displays moderate single-molecule magnets (SMMs) behavior. When difluorophenol co-ligands were used, a higher local axisymmetric pentagonal bipyramidal coordination geometry was observed in complex 2, which displays apparent slow magnetic relaxation behavior with a hysteresis temperature of up to 5 K. Further magnetic studies of diluted samples combined with ab initio calculations indicate that the high axiality plays a crucial role in suppressing quantum tunneling of magnetization (QTM) and consequently results in good slow magnetic relaxation behavior. Different fluoro-substituted phenoxyl co-ligands have phenoloxy oxygen atoms with different electrostatic potentials as well as a different number of phenoloxy coligands along the magnetic axis, resulting in different ligand field strengths and coordination symmetries.