Molecular Network Approach to Anisotropic Ising Lattices: Parsing Magnetization Dynamics in Er3+ Systems with 0-3-Dimensional Spin Interactivity.

We present a wide-ranging interrogation of the border between single-molecule and solid-state magnetism through a study of erbium-based Ising-type magnetic compounds with a fixed magnetic unit, using three different charge-balancing cations as the means to modulate the crystal packing environment. Properties rooted in the isolated spin Hamiltonian remain fixed, yet careful observation of the dynamics reveals the breakdown of this approximation in a number of interesting ways. First, differences in crystal packing lead to a striking 3 orders of magnitude suppression in magnetic relaxation rates, indicating a rich interplay between intermolecular interactions governed by the anisotropic Ising lattice stabilization and localized slow magnetic relaxation driven by the spin-forbidden nature of quantum tunneling of the f-electron-based magnetization. By means of diverse and rigorous physical methods, including temperature-dependent X-ray crystallography, field, temperature, and time-dependent magnetometry, and the application of a new magnetization fitting technique to quantify the magnetic susceptibility peakshape, we are able to construct a more nuanced view of the role nonzero-dimensional interactions can play in what are predominantly considered zero-dimensional magnetic materials. Specifically, we use low field susceptibility and virgin-curve analysis to isolate metamagnetic spin-flip transitions in each system with a field strength corresponding to the expected strength of the internal dipole-dipole lattice. This behavior is vital to a complete interpretation of the dynamics and is likely common for systems with such high anisotropy. This collective interactivity opens a new realm of possibility for molecular magnetic materials, where their unprecedented localized anisotropy is the determining factor in building higher dimensionality.

Quantifying superparamagnetic signatures in nanoparticle magnetite: a generalized approach for physically meaningful statistics and synthesis diagnostics.

Magnetization is a common measurable for characterizing bulk, nanoscale, and molecular materials, which can be quantified to high precision as a function of an applied external field. These data provide detailed information about a material's electronic structure, phase purity, and impurities, though interpreting this data can be challenging due to many contributing factors. In sub-single-domain particles of a magnetic material, an inherently time-dependent rotation of the entire particle spin becomes possible. This phenomenon, known as superparamagnetism (SPM), simultaneously represents a very early size-dependent property to be considered, while being one of the least explored in the current quantum materials era. This discrepancy is, at least in part, due to the need for models with less built-in complexity that can facilitate the generation of comparative data. In this work, we map an extensive dataset of variable-size SPM Fe3O4 (magnetite) to an intrinsic statistical model for their field-dependence. By constraining the SPM behavior to a probabilistic model, the data are apportioned to several decorrelated sources. From this, there is strong evidence that standard measures such as saturation magnetization, MS, are poor comparative parameters, being dependent on experimental knowledge and measurement of the magnetic mass. In contrast, parameters of the intrinsic probability distribution, such as the maximum susceptibility, χmax, are far better suited to describe the SPM behavior itself and do not propagate unknown magnetic mass error. By confining the data fitting to intrinsic variables of the model distribution, scaling parameters, and linear contributions, we find greater value in magnetic data, ultimately aiding potential synthesis diagnostics and prediction of new properties and functionality.

Size-Tunable Magnetite Nanoparticles from Well-Defined Iron Oleate Precursors.

The synthesis of iron oxide nanoparticles with control over size and shape has long been an area of research, with iron oleate being arguably the most successful precursor. Issues with reproducibility and versatility in iron oleate-based syntheses remain, however, in large part due to the mutable nature of its structure and stoichiometry. In this work, we characterize two new forms of iron oleate precursor that can be isolated in large quantities, show long-term stability, and have well-defined stoichiometry, leading to reproducible and predictable reactivity. Synthesis with these precursors is shown to produce iron oxide nanoparticles in a tunable size range of 4-16 nm with low size dispersity and properties consistent with magnetite in the superparamagnetic size regime.

Metamagnetic transition and a loss of magnetic hysteresis caused by electron trapping in monolayers of single-molecule magnet Tb2@C79N.

Realization of stable spin states in surface-supported magnetic molecules is crucial for their applications in molecular spintronics, memory storage or quantum information processing. In this work, we studied the surface magnetism of dimetallo-azafullerene Tb2@C79N, showing a broad magnetic hysteresis in a bulk form. Surprisingly, monolayers of Tb2@C79N exhibited a completely different behavior, with the prevalence of a ground state with antiferromagnetic coupling at low magnetic field and a metamagnetic transition in the magnetic field of 2.5-4 T. Monolayers of Tb2@C79N were deposited onto Cu(111) and Au(111) by evaporation in ultra-high vacuum conditions, and their topography and electronic structure were characterized by scanning tunneling microscopy and spectroscopy (STM/STS). X-ray photoelectron spectroscopy (XPS), in combination with DFT studies, revealed that the nitrogen atom of the azafullerene cage tends to avoid metallic surfaces. Magnetic properties of the (sub)monolayers were then studied by X-ray magnetic circular dichroism (XMCD) at the Tb-M4,5 absorption edge. While in bulk powder samples Tb2@C79N behaves as a single-molecule magnet with ferromagnetically coupled magnetic moments and blocking of magnetization at 28 K, its monolayers exhibited a different ground state with antiferromagnetic coupling of Tb magnetic moments. To understand if this unexpected behavior is caused by a strong hybridization of fullerenes with metallic substrates, XMCD measurements were also performed for Tb2@C79N adsorbed on h-BN|Rh(111) and MgO|Ag(100). The co-existence of two forms of Tb2@C79N was found on these substrates as well, but magnetization curves showed narrow magnetic hysteresis detectable up to 25 K. The non-magnetic state of Tb2@C79N in monolayers is assigned to anionic Tb2@C79N- species with doubly-occupied Tb-Tb bonding orbital and antiferromagnetic coupling of the Tb moments. A charge transfer from the substrate or trapping of secondary electrons are discussed as a plausible origin of these species.

High Blocking Temperature of Magnetization and Giant Coercivity in the Azafullerene Tb2 @C79 N with a Single-Electron Terbium-Terbium Bond.

The azafullerene Tb2 @C79 N is found to be a single-molecule magnet with a high 100-s blocking temperature of magnetization of 24 K and large coercivity. Tb magnetic moments with an easy-axis single-ion magnetic anisotropy are strongly coupled by the unpaired spin of the single-electron Tb-Tb bond. Relaxation of magnetization in Tb2 @C79 N below 15 K proceeds via quantum tunneling of magnetization with the characteristic time τQTM =16 462±1230 s. At higher temperature, relaxation follows the Orbach mechanism with a barrier of 757±4 K, corresponding to the excited states, in which one of the Tb spins is flipped.

Gadolinium based endohedral metallofullerene Gd2@C79N as a relaxation boosting agent for dissolution DNP at high fields.

We show increased dynamic nuclear polarization by adding a low dosage of a S = 15/2 Gd based endohedral metallofullerene (EMF) to DNP samples. By adding 60 µM Gd2@C79N, the nuclear polarization of 1H and 13C spins from 40 mM 4-oxo-TEMPO increases by approximately 40% and 50%, respectively, at 5 T and 1.2 K. Electron-electron double resonance (ELDOR) measurements show that the high spin EMF shortens the electron relaxation times and increases electron spectral diffusion leading to the increased DNP enhancement.