Single-Molecule Magnets

Abstract:
Single-molecule magnets (SMMs) with a large magnetization reversal barrier are predominated by the lanthanide systems due to their strong spin–orbit coupling (SOC). However, the transition metals have also emerged as potential contenders and the largest magnetic anisotropy has been identified for a cobalt system among any d-series-based SMMs (Bunting et al. Science 2018, 362, eaat7319). In this work, we have explored the magnetic anisotropy in highly axial ligand field systems of metallocene, having different d-subshell (3d4, 4d4, and 5d4). The wave function-based multireference methods including static and dynamic electron correlations have been employed to investigate the zero-field splitting (ZFS) parameters. Here, we report exceptionally large magnetic anisotropy for a 5d complex of [WCp2]0 with the highest energy barrier that is nearly twice as high as the previous record value for the Co complex. We have also observed that the axial ZFS parameter (D) is increasing down the group in the order of 3d < 4d < 5d, pertaining to a large SOC.

Abstract:

Abstract:
Single-molecule magnets (SMMs) based on transition metals have appeared as enticing targets exploiting magnetic anisotropy in 3d elements. Among transition metals, Co based SMMs are very prominent as they often exhibit a high spin-reversal barrier (Ueff), owing to their large unquenched orbital angular momentum. Employing the wave function-based multireference CASSCF/NEVPT2 calculations, herein we substantiate the zero-field splitting parameters of four mononuclear Co complexes and one of them has shown potential as an SMM. The mechanism of magnetic relaxation has been studied to understand the molecular origin of the slow relaxation of magnetization. The combination of suppressed quantum tunneling of magnetization (QTM) at the ground state and the high negative D value usually manifests SMM behavior in a zero-applied magnetic field. However, mere fulfillment of these conditions ensures little about their SMM behavior, as spin-vibrational coupling often plays spoilsport by lowering the spin relaxation channels. A detailed study accounting for all the 46 vibrational modes below the first-excited state for the prospective Co(II) complex, reveals one of the vibrational modes providing a lower spin relaxation pathway. This results in the development of an SMM with a Ueff value of 239.30 cm−1, decreased by ∼81 cm−1 from the value without spin-vibrational coupling.

Abstract:
With the ongoing efforts on synthesizing mononuclear single-ion magnets (SIMs) with promising applications in high-density data storage and spintronics devices, the linear or quasi-linear Fe(I) complexes emerge as the enticing candidates possessing large unquenched angular momentum. Herein, we have studied five experimentally synthesized linear Fe(I) complexes to uncover the origin of single-molecule magnetic behavior of these complexes. To begin with, we benchmarked the methodology on the experimentally and theoretically well-studied complex [Fe(C(SiMe₃)₃)₂]⁻¹(1) (SiMe₃ = trimethylsilyl), which is characterized with a large spin-reversal barrier of 226 cm^–1. Subsequently, the spin-phonon coupling coefficients are calculated for the low-frequency vibrational modes to understand the relaxation mechanism of the complex. Furthermore, the two Fe(I) complexes, that is, [Fe(cyIDep)₂]⁺¹(2) (cyIDep = 1,3-bis(2′,6′-diethylphenyl)-4,5-(CH₂)₄-imidazole-2-ylidene) and [Fe(sIDep)₂]⁺¹(3) (sIDep = 1,3-bis(2′,6′-diethylphenyl)-imidazolin-2-ylidene), are studied that are experimentally reported with no SIM behavior under ac or dc magnetic fields; however, they exhibit large opposite axial zero field splitting (−62.4 and +34.0 cm^–1, respectively) from ab initio calculations. We have unwrapped the origin of this contrasting observation between experiment and theory by probing their magnetic relaxation pathways and the pattern of d orbital splitting. Additionally, the two experimentally synthesized Fe(I) complexes, that is, [(η⁶-C₆H₆)FeAr*-3,5-Pr₂ⁱ] (4) (Ar*-3,5-Pr₂ⁱ = C₆H-2,6-(C₆H₂-2,4,6-Pr₃ⁱ)₂-3,5-Pr₂ⁱ) and [(CAAC)₂Fe]⁺¹(5) (CAAC = cyclic (alkyl) (amino)carbene), are investigated for SIM behavior, since there is no report on their magnetic anisotropy. To this end, complex 4 presents itself as the possible candidate for SIM.

Abstract:
With the ongoing effort to obtain mononuclear 3d-transition-metal complexes that manifest slow relaxation of magnetization and, hence, can behave as single-molecule magnets (SMMs), we have modeled 14 Fe(III) complexes based on an experimentally synthesized (PMe₃)₂FeCl₃ complex [J. Am. Chem. Soc. 2017, 139 (46), 16474–16477], by varying the axial ligands with group XV elements (N, P, and As) and equatorial halide ligands from F, Cl, Br, and I. Out of these, nine complexes possess large zero field splitting (ZFS) parameter D in the range of −40 to −60 cm^–1. The first-principles investigation of the ground-spin state applying density functional theory (DFT) and wave function-based multiconfigurations methods, e.g., SA-CASSCF/NEVPT2, are found to be quite consistent except for few delicate cases with near-degenerate spin states. In such cases, the hybrid B3LYP functional is found to be biased toward high-spin (HS) state. Altering the percentage of exact exchange admixed in the B3LYP functional leads to intermediate-spin (IS) ground state consistent with the multireference calculations. The origin of large zero field splitting (ZFS) in the Fe(III)-based trigonal bipyramidal (TBP) complexes is investigated. Furthermore, a number of complexes are identified with very small ΔG_HS–IS^adia. values indicating the possible spin-crossover phenomenon between the bistable spin states.

Abstract:
We present a comprehensive study of Er(trensal) single-ion magnets deposited in ultrahigh vacuum onto metallic surfaces. X-ray photoelectron spectroscopy reveals that the molecular structure is preserved after sublimation, and that the molecules are physisorbed on Au(111) while they are chemisorbed on a Ni thin film on Cu(100) single-crystalline surfaces. X-ray magnetic circular dichroism (XMCD) measurements performed on Au(111) samples covered with molecular monolayers held at temperatures down to 4 K suggest that the easy axes of the strongly anisotropic molecules are randomly oriented. Furthermore XMCD indicates a weak antiferromagnetic exchange coupling between the single-ion magnets and the ferromagnetic Ni/Cu(100) substrate. For the latter case, spin-Hamiltonian fits to the XMCD M(H) suggest a significant structural distortion of the molecules. Scanning tunneling microscopy reveals that the molecules are mobile on Au(111) at room temperature, whereas they are more strongly attached on Ni/Cu(100). X-ray photoelectron spectroscopy results provide evidence for the chemical bonding between Er(trensal) molecules and the Ni substrate. Density functional theory calculations support these findings and, in addition, reveal the most stable adsorption configuration on Ni/Cu(100) as well as the Ni–Er exchange path. Our study suggests that the magnetic moment of Er(trensal) can be stabilized via suppression of quantum tunneling of magnetization by exchange coupling to the Ni surface atoms. Moreover, it opens up pathways toward optical addressing of surface-deposited single-ion magnets.

Abstract:
We report on the synthesis, crystal structure and magnetic characterisation of the trinuclear, fluoride-bridged, molecular nanomagnet [Dy(hfac)₃(H₂O)–CrF₂(py)₄–Dy(hfac)₃(NO₃)] (1) (hfacH = 1,1,1,5,5,5-hexafluoroacetylacetone, py = pyridine) and a closely related dinuclear species [Dy(hfac)₄–CrF₂(py)₄]·½CHCl₃ (2). Element-specific magnetisation curves obtained on 1 by X-ray magnetic circular dichroism (XMCD) allow us to directly observe the field-induced transition from a ferrimagnetic to a ferromagnetic arrangement of the Dy and Cr magnetic moments. By fitting a spin-Hamiltonian model to the XMCD data we extract a weak antiferromagnetic exchange coupling of j = −0.18 cm⁻¹ between the Dy^III and Cr^III ions. The value found from XMCD is consistent with SQUID magnetometry and inelastic neutron scattering measurements. Furthermore, alternating current susceptibility and muon-spin relaxation measurements reveal that 1 shows thermally activated relaxation of magnetisation with a small effective barrier for magnetisation reversal of Δ_eff = 3 cm⁻¹. Density-functional theory calculations show that the Dy–Cr couplings originate from superexchange via the fluoride bridges.

Abstract:
We have investigated the magnetic properties of a recently synthesized dinuclear complex, [Cu₂(μ-OAc)₄(MeNHpy)₂], by broken-symmetry (BS) density functional (DFT) methodology. The complex has several pairs of magnetic orbitals. Therefore, we have explicitly calculated the overlap integral S_ab between the two natural magnetic orbitals, and found a value of 0.8589. Deviating from the common practice of approximating S_ab by 1 for the strongly delocalized systems, the computed value has been used in calculating the magnetic exchange coupling constant (J) from the two electron-two orbital BS model. The calculated J is −290 cm⁻¹, in excellent agreement with the observed value of −285 cm⁻¹. The contribution of the overlap between the orbitals of the two copper atoms to S_ab is negligibly small. Also, the calculated J value is a weakly varying function of the Cu–Cu distance. The last two observations confirm that the through-ligand superexchange phenomenon is responsible for the high magnetic exchange interaction in the Cu₂(μ-OAc)₄ complex(es). Furthermore, we have shown that the onset of intramolecular hydrogen bonding reduces the spin density on the bridging atoms and consequently the magnitude of J. This explains why the complex under investigation has a J value smaller than that of [Cu₂(μ-OAc)₄(H₂O)₂] (−299 cm⁻¹). While establishing this trend, we predict that the complex [Cu₂(μ-OAc)₄(py)₂] would have a higher J value, about −300 cm⁻¹.