Thermal behaviour of organic radicals and paramagnetic centres in chert: A case study of Bergeracois brown chert, Dordogne, France

In order to successfully understand the complex evolution of prehistoric societies, archaeologists require absolute dating tools, which are not only accurate but also widely applicable. Thermoluminescence (TL) dating is one such approach that has been successfully used to establish a general chronological framework for prehistoric sites and is particularly suited for use on heated lithic artefacts. Experiments conducted in this study have clearly shown the applicability of Electron Spin Resonance (ESR) isothermal modelling in combination with TL dating to constrain firing temperature. This expands the potential application for TL dating to include artefacts treated at low firing temperatures. The present study shows potential in terms of precision and accuracy for framing the “equivalent firing temperature”. At the same time, the comparison of the TL signal with the lattice-defects and aluminium centres invigorate the use of ESR dating on heated flint, especially with samples that have received low thermal treatment. The presence of organic matter in large quantity raises concern on the pyrolysis effect on the luminescence signal; however, the use of ESR isothermal and isochronal modelling could potentially lead to the ability to overcome current interferences of the organic radicals within the dating signal of TL.

Superexchange interactions in AgMF4 (M = Co, Ni, Cu) polymorphs

Magnetic properties of silver(II) compounds have been of interest in recent years. In covalent compounds, the main mechanism of interaction between paramagnetic sites is the superexchange via the connecting ligand. To date, little is known of magnetic interactions between Ag(II) cations and other paramagnetic centres. It is because only a few compounds bearing a Ag(II) cation and other paramagnetic transition metal cation are known from experimental work. Recently the high-pressure synthesis of ternary silver(II) fluoridometallates with 3d metal cations AgMF4 (M = Co, Ni, Cu) was predicted to be feasible. Here, we investigate the magnetic properties of these compounds in their diverse polymorphic forms. Using well-established computational methods we predict superexchange pathways in AgMF4 compounds, evaluate coupling constants and calculate the impact of the Ag(II) presence on superexchange between the other cations. The results indicate that the low-pressure form of AgCuF4, the only one composed of stacked layers like the parent AgF2, would show mainly Ag–Ag and Cu–Cu superexchange interactions. Upon compression, or with the nickel(II) cation, the Ag–M interactions in AgMF4 compounds are intensified, which is emphasized by an increase of Ag–M superexchange coupling constants and Ag–F–M angles. All the strongest Ag–M superexchange pathways are quasi-linear, leading to the formation of antiferromagnetic chains along the crystallographic directions. The impact of Ag(II) on M–M superexchange turns out to be moderate, due to factors connected to the crystal structure.

DEER and RIDME Measurements of the Nitroxide-Spin Labelled Copper-Bound Amine Oxidase Homodimer from Arthrobacter Globiformis

In the study of biological structures, pulse dipolar spectroscopy (PDS) is used to elucidate spin–spin distances at nanometre-scale by measuring dipole–dipole interactions between paramagnetic centres. The PDS methods of Double Electron Electron Resonance (DEER) and Relaxation Induced Dipolar Modulation Enhancement (RIDME) are employed, and their results compared, for the measurement of the dipolar coupling between nitroxide spin labels and copper-II (Cu(II)) paramagnetic centres within the copper amine oxidase from Arthrobacter globiformis (AGAO). The distance distribution results obtained indicate that two distinct distances can be measured, with the longer of these at c.a. 5 nm. Conditions for optimising the RIDME experiment such that it may outperform DEER for these long distances are discussed. Modelling methods are used to show that the distances obtained after data analysis are consistent with the structure of AGAO.

The range of antiferromagnetic coupling governs the conductivity: semiconducting behavior and ammonia gas sensing property of diamagnetic hexaradical-containing tetranuclear CoIII4 cluster and its nonradical congener

The long-range antiferromagnetic coupling impedes electron flow through hexaradical-containing tetranuclear CoIII4 complex (1), while nonradical-containing tetranuclear CoIII4 complex (2), with no paramagnetic centres, is a semiconductor and sensed NH3 efficiently at room temperature (25 °C).

A black-box approach to the construction of metal-radical multispin systems and analysis of their magnetic properties

The metal cation-induced transformation of nitronyl-nitroxide diradicals led to formation of the binuclear Mn(ii) and Ni(ii) complexes with six paramagnetic centres, their magnetic properties were analysed using high-level calculations.