EPR Study of the Mn-Doped Magnesium Titanate Ceramics

Manganese-doped magnesium titanate ceramic samples obtained by a solid-state reaction via sintering in the air from a mixture of MgO and TiO2 powders of different molar ratios were analyzed by electron paramagnetic resonance (EPR) technique. The EPR signals of Mn2+ ions (S = 5/2, І = 5/2) in crystal phases of MgO, Mg2TiO4, and MgTiO3 were detected. We have obtained the following spin Hamiltonian parameters for Mn2+ ions: g = 2.0015, A ~ 81 ∗ 10-4 cm-1 (in MgO phase); g = 2.0029, A ~ 73.8 ∗ 10-4 cm-1, b2 0 = 35 ∗ 10-4 cm-1 (in Mg2TiO4 phase); g = 2.004, A ~ 79 ∗ 10-4 cm-1, b2 0 = 165 ∗ 10-4 cm-1 (in MgTiO3 phase). Despite the presence of Mn4+ centers in both Mg2TiO4:Mn and MgTiO3:Mn ceramics confirmed by previous optical studies, no EPR signals related to Mn4+ ions (S = 3/2, І = 5/2) were found. The Mn2+ EPR signals are proposed as structural probes in manganese-doped magnesium titanate ceramics.

Identifying the "true" repeat unit of a copolymer using time-resolved electron paramagnetic resonance spectroscopy: a case study involving PNDIT2, NDI-T2 and T-NDI-T

Semiconducting polymers promise to revolutionise the way electronic devices can be built and deployed for a vast array of applications ranging from light-energy conversion to sensors to thermoelectric generators. Conjugated push-pull copolymers consisting of alternating donor and acceptor moieties are at the heart of these applications, due to the large tunability of their electronic structure. Hence, knowing the repeat unit and thus the chromophore of these materials is essential for a detailed understanding of the structure--function relationship of conjugated polymers used in organic electronics applications. Therefore, spectroscopic tools providing the necessary molecular resolution that allows to discriminate between different building blocks and to decide which one actually resembles the electronic structure of the polymer are of utmost importance. Time-resolved electron paramagnetic resonance (TREPR) spectroscopy is both, perfectly suited for this task and clearly superior to optical spectroscopy, particularly when supported by quantum-chemical calculations. This is due to its molecular resolution and unique capability of using light-induced triplet states to probe the electronic structure as well as the impact of the local environment. Here, we demonstrate the power of this approach for the polymer PNDIT2 (poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)}) revealing NDI-T2 unambiguously as the "true" repeat unit of the polymer, representing the chromophore. The alternative building block T-NDI-T has a markedly different electronic structure. These results are of high importance for the rational design of conjugated polymers for organic electronics applications.

Application of time-resolved electron paramagnetic resonance spectroscopy in the mechanistic study of thermally activated delayed fluorescence (TADF) materials

Triplet exciton harvesting is crucial in organic light emitting diodes (OLEDs), because the triplet states produced by electron and hole recombination is up to 75% of the total excitons, whereas...

Dipolar pathways in dipolar EPR spectroscopy

Dipolar electron paramagnetic resonance (EPR) experiments such as double electron--electron resonance (DEER) measure distributions of nanometer-scale distances between unpaired electrons, which provide valuable information for structural characterization of proteins and...

A radical approach to radicals

Nitroxide radicals are characterized by a long-lived spin-unpaired electronic ground state and are strongly sensitive to their chemical surroundings. Combined with electron paramagnetic resonance spectroscopy, these electronic features have led to the widespread application of nitroxide derivatives as spin labels for use in studying protein structure and dynamics. Site-directed spin labelling requires the incorporation of nitroxides into the protein structure, leading to a new protein–ligand molecular model. However, in protein crystallographic refinement nitroxides are highly unusual molecules with an atypical chemical composition. Because macromolecular crystallography is almost entirely agnostic to chemical radicals, their structural information is generally less accurate or even erroneous. In this work, proteins that contain an example of a radical compound (Chemical Component Dictionary ID MTN) from the nitroxide family were re-refined by defining its ideal structural parameters based on quantum-chemical calculations. The refinement results show that this procedure improves the MTN ligand geometries, while at the same time retaining higher agreement with experimental data.

Study of Endogenous Paramagnetic Centers in Biological Systems from Different Areas

Plant leaves (Eldar pine (Pinus eldarica M.), fig (Ficus carica L.), and olive (Olea europaea L.)), collected in territories with different ecological conditions, of the Absheron Peninsula (Azerbaijan Republic) were studied by electron paramagnetic resonance spectroscopy (EPR). The generation of nanophase iron oxide magnetic particles in biological systems under the influence of stress factors was revealed. It was found that the process of biomineralization plays a role in the formation of biogenic iron oxide magnetic nanoparticles in plants and the generation of magnetite crystals in biological tissues, and stress factors have a stimulating effect on this phenomenon.

A Rudimentary X band CW-EPR Spectrometer Based on FPGA

A rudimentary Electron Paramagnetic Resonance (EPR) spectrometer is design using a field programmable gate array (FPGA) equipped with two digital-to-analog (DAC) and two analog-to-digital (ADC) channels. The single stage heterodyne setup operates at X band frequencies and is used to detect EPR signals from 2,2-diphenyl-1-picrylhydrazyl (DPPH) in a loop-gap resonator. We design the loop gap resonator with 3 loops 2 gaps for high field homogeneity and moderate Q-factor. The resonator is coupled capacitively to the coaxial cable and is designed to have an unloaded resonant frequency of 8.856 GHz with a Q-factor of 646.0 when critically coupled. The loaded resonant frequency is reported to be 8.668 GHz with a Q-factor of 615.8. Using this setup, EPR signal is successfully detected at 311.4 mT and 8.688 GHz with an experimental g-factor of 1.99450.0012, which is very near to the standard value for DPPH.