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The development and technological applications of molecular spin systems require versatile experimental techniques to characterize and control their static and dynamic magnetic properties. In the latter case, bulk spectroscopic and magnetometric techniques, such as AC magnetometry and pulsed electron paramagnetic resonance, are usually employed, showing high sensitivity, wide dynamic range, and flexibility. They are based on creating a nonequilibrium state either by changing the magnetic field or by applying resonant microwave radiation. Another possible source of perturbation is a laser pulse that rapidly heats the sample. This approach has proven to be one of the most useful techniques for studying the kinetics and mechanism of chemical and biochemical reactions. Inspired by these works, we propose an inductive detection of temperature-induced magnetization dynamics as applied to the study of molecular spin systems and describe the general design and construction of a particular induction probehead, taking into account the constraints imposed by the cryostat and electromagnet. To evaluate the performance, several coordination compounds of VO2+, Co2+, and Dy3+ were investigated using low-energy pulses of a terahertz free electron laser of the Novosibirsk free electron laser facility as a heat source. All measured magnetization dynamics were qualitatively or quantitatively described using a proposed basic theoretical model and compared with the data obtained by alternating current magnetometry. Based on the results of the research, the possible scope of applications of inductive detection and its advantages and disadvantages in comparison with standard methods are discussed. [ABSTRACT FROM AUTHOR]

The application of terahertz (THz) science in industrial technology and scientific research requires efficient THz detectors. Such detectors should be able to operate under various external conditions and conform to existing geometric constraints in the required application. Pyroelectric THz detectors are among the best candidates. This is due to their versatility, outstanding performance, ease of fabrication, and robustness. In this paper, we propose a compact pyroelectric detector based on a bioriented poled polyvinylidene difluoride film coated with sputtered metal electrodes for in situ absorption measurement at cryogenic temperature. The detector design was optimized for the registration system of the electron paramagnetic resonance (EPR) endstation of the Novosibirsk Free Electron Laser facility. Measurements of the detector response to pulsed THz radiation at different temperatures and electrode materials showed that the response varies with both the temperature and the type of electrode material used. The maximum signal level corresponds to the temperature range of 10–40 K, in which the pyroelectric coefficient of the PVDF film also has a maximum value. Among the three coatings studied, namely indium tin oxide (ITO), Au, and Cu/Ni, the latter has the highest increase in sensitivity at low temperature. The possibility of using the detectors for in situ absorption measurement was exemplified using two typical molecular spin systems, which exhibited a transparency of 20–30% at 76.9 cm−1 and 5 K. Such measurements, carried out directly in the cryostat with the main recording system and sample fully configured, allow precise control of the THz radiation parameters at the EPR endstation. [ABSTRACT FROM AUTHOR]

A new binuclear "paddle-wheel" complex, [Co2(bhbz)4(EtOH)2]·4EtOH (1, Hbhbz-3,5-di(tert-butyl)-4-hydroxybenzoic acid); an isostructural zinc complex (2); a and magnetically diluted sample of [Zn1.93Co0.07(bhbz)4(EtOH)2]·4EtOH (3) were obtained. Molecular structures of 1 and 2 were determined by single-crystal X-ray diffraction. DFT calculations for 1 indicate strong Co-Co antiferromagnetic exchange interactions in the binuclear fragment. It was shown that when one paramagnetic ion in the binuclear molecule is replaced by a diamagnetic zinc(II) ion, the remaining cobalt(II) ion can be considered as an isolated center with magnetic anisotropy, the parameters of which are determined by ab initio calculations. Magnetic properties for samples 1 and 3 were investigated and analyzed in detail. [ABSTRACT FROM AUTHOR]

Copper(II)–nitroxide based Cu(hfac)2LR compounds exhibit unusual magnetic behavior that can be induced by various stimuli. In many aspects, the magnetic phenomena observed in Cu(hfac)2LR are similar to classical spin-crossover behavior. However, these phenomena originate from polynuclear exchange-coupled spin clusters Cu2+–O˙–N< or >N–˙O–Cu2+–O˙–N<. Such peculiarities may result in additional multifunctionality of Cu(hfac)2LR compounds, making them promising materials for spintronic applications. Herein, we investigate the Cu(hfac)2LMeMe material, which demonstrates a three-step temperature-induced magnetostructural transition between high-temperature, low-temperature, and intermediate states, as revealed by magnetometry. Two main steps were resolved using variable-temperature Fourier-transform infrared and Q-band electron paramagnetic resonance (EPR) spectroscopies. The intermediate-temperature states (∼40–90 K) are characterized by the coexistence of two types of copper(II)–nitroxide clusters, corresponding to the low-temperature and high-temperature phases. High-field EPR experiments revealed the effect of partial alignment of Cu(hfac)2LMeMe microcrystals in a strong (>20 T) magnetic field. This effect was used to unveil the structural features of the low-temperature phase of Cu(hfac)2LMeMe, which were inaccessible using single-crystal X-ray diffraction (XRD) technique. In particular, high-field EPR allowed us to determine the relative direction of the Jahn–Teller axes in CuO6 and CuO4N2 units. [ABSTRACT FROM AUTHOR]

A new 1D-coordination polymer [Co(Piv)2(NH2(CH2)6NH2)]n (1, Piv is Me3CCO2− anion) was obtained, the mononuclear fragments {Co(O2CR)2} within which are linked by μ-bridged molecules of hexamethylenediamine (NH2(CH2)6NH2). For this compound, two different monoclinic C2/c (α-1) and P2/n (β-1) phases were found at room temperature by single-crystal X-ray diffraction analysis, with a similar structure of chains and their packages in unit cells. The low-temperature phase (γ-1) of crystal 1 at 150 K corresponds to the triclinic space group P-1. As the temperature decreases, the structural phase transition (SPT) in the α-1 and β-1 crystals is accompanied by an increase in the crystal packing density caused by the rearrangements of both H-bonds and the nearest ligand environment of the cobalt atom ("octahedral CoN2O4 around the metal center at room temperature" → "pseudo-tetrahedral CoN2O2 at 150 K"). The SPT was confirmed by DSC in the temperature range 210–150 K; when heated above 220 K, anomalies in the behavior of the heat flow are observed, which may be associated with the reversibility of SPT; endo effects are observed up to 300 K. The SPT starts below 200 K. At 100 K, a mixture of phases was found in sample 1: 27% α-1 phase, 61% γ-1 phase. In addition, at 100 K, 12% of the new δ-1 phase was detected, which was identified from the diffraction pattern at 260 K upon subsequent heating: the a,b,c-parameters and unit cell volume are close to the structure parameters of γ-1, and the values of the α,β,γ-angles are significantly different. Further heating leads to a phase transition from δ-1 to α-1, which both coexist at room temperature. According to the DC magnetometry data, during cooling and heating, the χMT(T) curves for 1 form a hysteresis loop with ~110 K, in which the difference in the χMT values reaches 9%. Ab initio calculations of the electronic structure of cobalt(II) in α-1 and γ-1 have been performed. Based on the EPR data at 10 K and the ab initio calculations, the behavior of the χMT(T) curve for 1 was simulated in the temperature range of 2–150 K. It was found that 1 exhibits slow magnetic relaxation in a field of 1000 Oe. [ABSTRACT FROM AUTHOR]

Advanced atomically resolved characterization methods unveil the mechanism of a promising photocatalytic Co@MOF(Ti) system for H2 production. The combination of X-ray absorption spectroscopy (XAS) and electron paramagnetic resonance (EPR) experiments allows for the characterization of atomic and electronic rearrangements in the photoinduced species. This information provides the basis for the optimization of photocatalyst design. [ABSTRACT FROM AUTHOR]

Breathing crystals based on polymer-chain complexes of Cu(hfac)2 (hfac = hexafluoroacetylacetonate) with nitronyl nitroxides represent a new type of molecular magnetic sensors, exhibiting thermally and light-induced structural rearrangements in the spin clusters Cu ← (O∸N<)n accompanied by magnetic anomalies. To shed light on the driving forces of the rearrangements a method for the synthesis of sterically hindered 4-oxo-3,4-dihydro-2H-pyrrole-N-oxides (nitronyl ketones) structurally mimicking nitronyl nitroxides in breathing crystals has been determined. This method employs palladium-catalyzed cross-coupling of 3,3,4-trimethyl-4-nitropentanoic acid chloride with 4-stannylpyrazoles, leading to the formation of nitroketones followed by soft reduction into hydroxylamines, that then undergo self-initiated cyclization into the corresponding nitrones. The radical oxidation of the latter finally yields the target nitronyl ketones. An X-ray diffraction analysis of the nitronyl ketones confirms that their structural characteristics are close to those of the corresponding nitronyl nitroxides. Moreover, upon reaction with Cu(hfac)2, diamagnetic nitronyl ketones form polymer-chain complexes with a 'head-to-tail' motif and a structure similar to their analogues containing paramagnetic nitronyl nitroxides. Finally, it has been found that one of the complexes with nitronyl ketones does manifest a purely structural phase transition similar to its copper-nitroxide analogue, but at the same time it does not manifest any signs of a magneto-structural transition characteristic for breathing crystals where a Jahn-Teller axis in the coordination units CuNO4(O∸N<) is flipped. This observation strongly confirms the crucial role of the exchange interactions between spins of copper and nitroxide for the origin of magneto-structural anomalies in breathing crystals. [ABSTRACT FROM AUTHOR]

The d-group Kramers ions, having strong zero field splitting (ZFS) with axial symmetry and a negative D value for the ZFS Hamiltonian, are widely considered as candidates for use as single molecular magnets (SMMs). An important need is the means to switch the SMM between its states in a reasonably short and predictable period of time, which is generally not available. We propose an approach, Zeeman–far infrared (ZeFIR) double resonance, in which circularly polarized alternating magnetic fields in the far infrared (FIR) range induce selective magnetic dipole transitions between different Kramers doublets of the SMM and polarized microwave (mw) pulses transfer excitation inside the upper Kramers doublet. A combination of FIR and mw pulses allows unidirectional switching between +S and −S states of the ion. The proposed approach is considered for a model quartet system with total spin S = 3/2, which seems to be the most promising object for selective resonance manipulations of its states by circularly polarized radiation. [ABSTRACT FROM AUTHOR]

Copper(II)-nitroxide based molecular magnets exhibit spin-crossover-like spin state switching, which is topical in field of molecular magnetism. However, establishing reliable structure-property relationships in these systems is still challenging, especially regarding the light-induced switching of spin states. In this paper, we report the investigation of photoswitching and relaxation in a series of heterospin Cu(hfac) 2 L R complexes with pyridine-based nitroxide ligands (L R ), which belong to this family of materials. Using electron paramagnetic resonance (EPR) for detection, we demonstrate very long lifetimes of photoinduced spin states at liquid helium temperatures (<15 K), where relaxation to the ground state does not exceed 15% within two hours. At the same time, the efficiency of photoswitching strongly depends on the structure of the radical ligand in this series: the bulkier the ligand, the smaller the fraction of heterospin clusters that undergo photoswitching. These findings expand the understanding of mechanisms and factors behind photoswitching and relaxation in copper(II)-nitroxide molecular magnets and aid in further research aiming to optimize their functional properties.

Copper(II)-nitroxide based Cu(hfac) 2 L R compounds exhibit unusual magnetic behavior that can be induced by various stimuli. In many aspects, the magnetic phenomena observed in Cu(hfac) 2 L R are similar to classical spin-crossover behavior. However, these phenomena originate from polynuclear exchange-coupled spin clusters Cu 2+ -O˙-N< or >N-˙O-Cu 2+ -O˙-N<. Such peculiarities may result in additional multifunctionality of Cu(hfac) 2 L R compounds, making them promising materials for spintronic applications. Herein, we investigate the Cu(hfac) 2 L MeMe material, which demonstrates a three-step temperature-induced magnetostructural transition between high-temperature, low-temperature, and intermediate states, as revealed by magnetometry. Two main steps were resolved using variable-temperature Fourier-transform infrared and Q-band electron paramagnetic resonance (EPR) spectroscopies. The intermediate-temperature states (∼40-90 K) are characterized by the coexistence of two types of copper(II)-nitroxide clusters, corresponding to the low-temperature and high-temperature phases. High-field EPR experiments revealed the effect of partial alignment of Cu(hfac) 2 L MeMe microcrystals in a strong (>20 T) magnetic field. This effect was used to unveil the structural features of the low-temperature phase of Cu(hfac) 2 L MeMe , which were inaccessible using single-crystal X-ray diffraction (XRD) technique. In particular, high-field EPR allowed us to determine the relative direction of the Jahn-Teller axes in CuO 6 and CuO 4 N 2 units.