EMR-related problems at the interface between the crystal field Hamiltonians and the zero-field splitting Hamiltonians

The interface between optical spectroscopy, electron magnetic resonance (EMR), and magnetism of transition ions forms the intricate web of interrelated notions. Major notions are the physical Hamiltonians, which include the crystal field (CF) (or equivalently ligand field (LF)) Hamiltonians, and the effective spin Hamiltonians (SH), which include the zero-field splitting (ZFS) Hamiltonians as well as to a certain extent also the notion of magnetic anisotropy (MA). Survey of recent literature has revealed that this interface, denoted CF (LF) ↔ SH (ZFS), has become dangerously entangled over the years. The same notion is referred to by three names that are not synonymous: CF (LF), SH (ZFS), and MA. In view of the strong need for systematization of nomenclature aimed at bringing order to the multitude of different Hamiltonians and the associated quantities, we have embarked on this systematization. In this article, we do an overview of our efforts aimed at providing a deeper understanding of the major intricacies occurring at the CF (LF) ↔ SH (ZFS) interface with the focus on the EMR-related problems for transition ions

Determination of Crystal-Field Energy Levels and Temperature Dependence of Magnetic Susceptibility for Dy³⁺ in [Dy₂Pd] Heterometallic Complex

This study is the first in a series of experimental and theoretical investigations of the crystal-field (CF) energy levels obtained from optical electronic spectra for selected heterometallic 4f-3d compounds intensively studied for the development of novel single-molecule magnets (SMMs). An intriguing question is why the [{Dy^III(hfac)₃}₂Cu^II(dpk)₂] (abbreviated as [Dy₂Cu]; Hhfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione, Hdpk = di-2-pyridyl ketoxime) has antiferromagnetic coupling, whereas [Gd₂Cu] and heavy [Ln₂Cu] systems usually show ferromagnetic coupling. As the first step to explain this peculiarity, the recently synthesized complex, [Dy₂Pd], is investigated. This complex is isostructural with [Dy₂Cu] yet contains the diamagnetic Pd ion instead of the magnetic Cu­(II) ion. Experimental energy levels of Dy³⁺ ions in the powder [Dy₂Pd] sample were determined from the 4.2 K absorption spectra. CF analysis was performed yielding the fitted free ion and CF parameters. The number of freely varied parameters was restricted using the superposition model. The fittings yield very satisfactory agreement between the experimental and the calculated energy levels (<i>rms</i> = 12.0 cm^–1). The energies and exact composition of the state vector for the ground multiplet ⁶H_15/2 of Dy³⁺ are determined. These results are used for the simulation of the temperature dependence of the magnetic susceptibility, which enables the theoretical interpretation of the experimentally measured magnetic susceptibility in the range 1.8–300 K for the [Dy₂Pd] complex. This study provides background for the subsequent investigation of the magnetic exchange interactions in the pertinent heterometallic complexes

Toxicity Mechanism of Low Doses of NaGdF4:Yb3+,Er3+ Upconverting Nanoparticles in Activated Macrophage Cell Lines

Gadolinium-doped nanoparticles (NPs) are regarded as promising luminescent probes. In this report, we studied details of toxicity mechanism of low doses of NaGdF4-based fluorescent nanoparticles in activated RAW264.7, J774A.1 macrophages. These cell lines were specifically sensitive to the treatment with nanoparticles. Using nanoparticles of three different sizes, but with a uniform zeta potential (about &minus;11 mV), we observed rapid uptake of NPs by the cells, resulting in the increased lysosomal compartment and subsequent superoxide induction along with a decrease in mitochondrial potential, indicating the impairment of mitochondrial homeostasis. At the molecular level, this led to upregulation of proapoptotic Bax and downregulation of anti-apoptotic Bcl-2, which triggered the apoptosis with phosphatidylserine externalization, caspase-3 activation and DNA fragmentation. We provide a time frame of the toxicity process by presenting data from different time points. These effects were present regardless of the size of nanoparticles. Moreover, despite the stability of NaGdF4 nanoparticles at low pH, we identified cell acidification as an essential prerequisite of cytotoxic reaction using acidification inhibitors (NH4Cl or Bafilomycin A1). Therefore, approaching the evaluation of the biocompatibility of such materials, one should keep in mind that toxicity could be revealed only in specific cells. On the other hand, designing gadolinium-doped NPs with increased resistance to harsh conditions of activated macrophage phagolysosomes should prevent NP decomposition, concurrent gadolinium release, and thus the elimination of its toxicity