Dipolar Coupling as a Mechanism for Fine Control of Magnetic States in ErCOT-Alkyl Molecular Magnets

The design of molecular magnets has progressed greatly by taking advantage of the ability to impart successive perturbations and control vibronic transitions in 4fn systems through the careful manipulation of the crystal field. Herein, we control the orientation and rigidity of two dinuclear ErCOT-based molecular magnets: the inversion-symmetric bridged [ErCOT­(μ-Me)­(THF)]2 (2) and the nearly linear Li­[(ErCOT)2(μ-Me)3] (3). The conserved anisotropy of the ErCOT synthetic unit facilitates the direction of the arrangement of its magnetic anisotropy for the purposes of generating controlled internal magnetic fields, improving control of the energetics and transition probabilities of the electronic angular momentum states with exchange biasing via dipolar coupling. This control is evidenced through the introduction of a second thermal barrier to relaxation operant at low temperatures that is twice as large in 3 as in 2. This barrier acts to suppress through-barrier relaxation by protecting the ground state from interacting with stray local fields while operating at an energy scale an order of magnitude smaller than the crystal field term. These properties are highlighted when contrasted against the mononuclear structure ErCOT­(Bn)­(THF)2 (1), in which quantum tunneling of the magnetization processes dominate, as demonstrated by magnetometry and ab initio computational methods. Furthermore, far-infrared magnetospectroscopy measurements reveal that the increased rigidity imparted by successive removal of solvent ligands when adding bridging methyl groups, along with the increased excited state purity, severely limits local spin–vibrational interactions that facilitate magnetic relaxation, manifesting as longer relaxation times in 3 relative to those in 2 as temperature is increased

Dipolar Coupling as a Mechanism for Fine Control of Magnetic States in ErCOT-Alkyl Molecular Magnets

The design of molecular magnets has progressed greatly by taking advantage of the ability to impart successive perturbations and control vibronic transitions in 4fn systems through the careful manipulation of the crystal field. Herein, we control the orientation and rigidity of two dinuclear ErCOT-based molecular magnets: the inversion-symmetric bridged [ErCOT­(μ-Me)­(THF)]2 (2) and the nearly linear Li­[(ErCOT)2(μ-Me)3] (3). The conserved anisotropy of the ErCOT synthetic unit facilitates the direction of the arrangement of its magnetic anisotropy for the purposes of generating controlled internal magnetic fields, improving control of the energetics and transition probabilities of the electronic angular momentum states with exchange biasing via dipolar coupling. This control is evidenced through the introduction of a second thermal barrier to relaxation operant at low temperatures that is twice as large in 3 as in 2. This barrier acts to suppress through-barrier relaxation by protecting the ground state from interacting with stray local fields while operating at an energy scale an order of magnitude smaller than the crystal field term. These properties are highlighted when contrasted against the mononuclear structure ErCOT­(Bn)­(THF)2 (1), in which quantum tunneling of the magnetization processes dominate, as demonstrated by magnetometry and ab initio computational methods. Furthermore, far-infrared magnetospectroscopy measurements reveal that the increased rigidity imparted by successive removal of solvent ligands when adding bridging methyl groups, along with the increased excited state purity, severely limits local spin–vibrational interactions that facilitate magnetic relaxation, manifesting as longer relaxation times in 3 relative to those in 2 as temperature is increased

Dipolar Coupling as a Mechanism for Fine Control of Magnetic States in ErCOT-Alkyl Molecular Magnets

The design of molecular magnets has progressed greatly by taking advantage of the ability to impart successive perturbations and control vibronic transitions in 4fn systems through the careful manipulation of the crystal field. Herein, we control the orientation and rigidity of two dinuclear ErCOT-based molecular magnets: the inversion-symmetric bridged [ErCOT­(μ-Me)­(THF)]2 (2) and the nearly linear Li­[(ErCOT)2(μ-Me)3] (3). The conserved anisotropy of the ErCOT synthetic unit facilitates the direction of the arrangement of its magnetic anisotropy for the purposes of generating controlled internal magnetic fields, improving control of the energetics and transition probabilities of the electronic angular momentum states with exchange biasing via dipolar coupling. This control is evidenced through the introduction of a second thermal barrier to relaxation operant at low temperatures that is twice as large in 3 as in 2. This barrier acts to suppress through-barrier relaxation by protecting the ground state from interacting with stray local fields while operating at an energy scale an order of magnitude smaller than the crystal field term. These properties are highlighted when contrasted against the mononuclear structure ErCOT­(Bn)­(THF)2 (1), in which quantum tunneling of the magnetization processes dominate, as demonstrated by magnetometry and ab initio computational methods. Furthermore, far-infrared magnetospectroscopy measurements reveal that the increased rigidity imparted by successive removal of solvent ligands when adding bridging methyl groups, along with the increased excited state purity, severely limits local spin–vibrational interactions that facilitate magnetic relaxation, manifesting as longer relaxation times in 3 relative to those in 2 as temperature is increased

Electronic Structure of Three-Coordinate Fe^II and Co^II β‑Diketiminate Complexes

The β-diketiminate supporting group, [ArNCRCHCRNAr]−, stabilizes low coordination number complexes. Four such complexes, where R = tert-butyl, Ar = 2,6-diisopropylphenyl, are studied: (nacnactBu)ML, where M = FeII, CoII and L = Cl, CH3. These are denoted FeCl, FeCH3, CoCl, and CoCH3 and have been previously reported and structurally characterized. The two FeII complexes (S = 2) have also been previously characterized by Mössbauer spectroscopy, but only indirect assessment of the ligand-field splitting and zero-field splitting (zfs) parameters was available. Here, EPR spectroscopy is used, both conventional field-domain for the CoII complexes (with S = 3/2) and frequency-domain, far-infrared magnetic resonance spectroscopy (FIRMS) for all four complexes. The CoII complexes were also studied by magnetometry. These studies allow accurate determination of the zfs parameters. The two FeII complexes are similar with nearly axial zfs and large magnitude zfs given by D = −37 ± 1 cm–1 for both. The two CoII complexes likewise exhibit large and nearly axial zfs, but surprisingly, CoCl has positive D = +55 cm–1 while CoCH3 has negative D = −49 cm–1. Theoretical methods were used to probe the electronic structures of the four complexes, which explain the experimental spectra and the zfs parameters

Magnetic field tuning of crystal field levels and vibronic states in Spin-ice Ho2_2Ti2_2O7_7 observed in far-infrared reflectometry

Low temperature optical spectroscopy in applied magnetic fields provides clear evidence of magnetoelastic coupling in the spin ice material Ho$_2$Ti$_2$O$_7$. In far-IR reflectometry measurements, we observe field dependent features around 30, 61, 72 and 78~meV, energies corresponding to crystal electronic field (CEF) doublets. The calculations of the crystal-field Hamiltonian model confirm that the observed features in IR spectra are consistent with magnetic-dipole-allowed excitations from the ground state to higher $^5$I$_8$ CEF levels. We present the CEF parameters that best describe our field-dependent IR reflectivity measurements. Additionally, we identify a weak field-dependent shoulder near one of the CEF doublets. This indicates that this level is split even in zero-field, which we associate with a vibronic bound state. Modeling of the observed splitting shows that the phonon resides at slightly lower energy compared to the CEF level that it couples to, which is in contrast with previously published inelastic neutron measurements. The magnetic field dependence of the vibronic state shows a gradual decoupling of the phonon with the CEF level as it shifts. This approach should work in pyrochlores and other systems that have magnetic dipole transitions in the IR spectroscopic range, which can elucidate the presence and the ability to tune the nature of vibronic states in a wide variety of materials

Large Magnetic Anisotropy in Mono- and Binuclear cobalt(II) Complexes: The Role of the Distortion of the Coordination Sphere in Validity of the Spin-Hamiltonian Formalism

To get a better insight into understanding the factors affecting the enhancement of the magnetic anisotropy in single molecule (single ion) magnets, two cobalt(II) complexes based on a tridentate ligand 2,6-di(thiazol-2-yl)pyridine substituted at the 4-position with N-methyl-pyrrol-2-yl have been synthesized and studied by X-ray crystallography, AC and DC magnetic data, FIRMS and HFEPR spectra, and theoretical calculations. The change of the counteranion in starting Co(II) salts results in the formation of pentacoordinated mononuclear [Co(mpyr-dtpy)Cl2]·2MeCN (1) complex and binuclear [Co(mpyr-dtpy)2][Co(NCS)4] (2) compound. The observed marked distortion of trigonal bipyramid geometry in 1 and cationic octahedral and anionic tetrahedral units in 2 brings up a question about the validity of the spin-Hamiltonian formalism and the possibility of determining the value and sign of the zero-field splitting D parameter. Both complexes exhibit field-induced slow magnetic relaxation with two or three relaxation channels at BDC = 0.3 T. The high-frequency relaxation time in the reciprocal form τ(HF)−1 = CTn develops according to the Raman relaxation mechanism (for 2, n = 8.8) and the phonon-bottleneck-like mechanism (for 1, n = 2.3). The high-frequency relaxation time at T = 2.0 K and BDC = 0.30 T is τ(HF) = 96 and 47 μs for 1 and 2, respectively

Coligand Effects on the Field-Induced Double Slow Magnetic Relaxation in Six-Coordinate Cobalt(II) Single-Ion Magnets (SIMs) with Positive Magnetic Anisotropy

Two mononuclear cobalt­(II) compounds of formula [Co­(dmphen)2(OOCPh)]­ClO4·1/2H2O·1/2CH3OH (1) and [Co­(dmbipy)2(OOCPh)]­ClO4 (2) (dmphen = 2,9-dimethyl-1,10-phenanthroline, dmbipy = 6,6′-dimethyl-2,2′-bipyridine and HOOCPh = benzoic acid) are prepared and magnetostructurally investigated. Each cobalt­(II) ion is six-coordinate with a distorted octahedral CoN4O2 environment. The complex cations are interlinked leading to supramolecular chains (1) and pairs (2) that grow along the crystallographic c-axis with racemic mixtures of (Δ,Λ)-Co units. FIRMS allowed us to directly measure the zero-field splitting between the two lowest Kramers doublets, which led to axial anisotropy values of 58.3 cm–1 ≤ D < 60.7 cm–1 (1) and 63.8 cm–1 ≤ D –1 (2). HFEPR spectra of polycrystalline samples of 1 and 2 at low temperatures confirm the positive sign of D and provide an estimate of the E/D quotient [0.147/0.187 (1) and 0.052 (2)]. Detailed ac and dc magnetic studies reveal that 1 and 2 are new examples of field-induced single-ion magnets (SIMs) with small transversal anisotropy. CASSCF/NEVPT2 calculations support these results. Two Orbach processes or one Orbach plus a direct relaxation mechanism provide similar agreements with the nonlinear experimental Arrhenius plots at Hdc = 500 and 2500 G for 1. Two independent relaxation processes occur in 2, but in contrast to 1, an observed linear dependence of ln­(τ) vs 1/T substantiates Orbach processes against the most widely proposed Raman and direct mechanisms. The analysis of each relaxation process in 2 provided values for Ea and τ0 that are very close to those found for 1, validating the predominant role of the Orbach relaxations in both compounds and, probably, also in other cobalt­(II) SIMs. A mechanism based on a spin-phonon coupling is proposed to account for the SIM behavior in 1 and 2 with any Raman or direct processes being discarded

Spectroscopic and Magnetic Studies of Co(II) Scorpionate Complexes: Is There a Halide Effect on Magnetic Anisotropy?

The observation of single-molecule magnetism in transition-metal complexes relies on the phenomenon of zero-field splitting (ZFS), which arises from the interplay of spin–orbit coupling (SOC) with ligand-field-induced symmetry lowering. Previous studies have demonstrated that the magnitude of ZFS in complexes with 3d metal ions is sometimes enhanced through coordination with heavy halide ligands (Br and I) that possess large free-atom SOC constants. In this study, we systematically probe this “heavy-atom effect” in high-spin cobalt(II)–halide complexes supported by substituted hydrotris(pyrazol-1-yl)borate ligands (TptBu,Me and TpPh,Me). Two series of complexes were prepared: [CoIIX(TptBu,Me)] (1-X; X = F, Cl, Br, and I) and [CoIIX(TpPh,Me)(HpzPh,Me)] (2-X; X = Cl, Br, and I), where HpzPh,Me is a monodentate pyrazole ligand. Examination with dc magnetometry, high-frequency and -field electron paramagnetic resonance, and far-infrared magnetic spectroscopy yielded axial (D) and rhombic (E) ZFS parameters for each complex. With the exception of 1-F, complexes in the four-coordinate 1-X series exhibit positive D-values between 10 and 13 cm–1, with no dependence on halide size. The five-coordinate 2-X series exhibit large and negative D-values between −60 and −90 cm–1. Interpretation of the magnetic parameters with the aid of ligand-field theory and ab initio calculations elucidated the roles of molecular geometry, ligand-field effects, and metal–ligand covalency in controlling the magnitude of ZFS in cobalt–halide complexes