Spin-Crossover and Slow Magnetic Relaxation Behavior in Hexachlororhenate(IV) Salts of Mn(III) Complexes [Mn(5-Hal-sal2323)]2[ReCl6] (Hal = Cl, Br).

The cationic complexes of Mn(III) with the 5-Hal-sal2323 (Hal = Cl, Br) ligands and a paramagnetic doubly charged counterion [ReCl6]2- have been synthesized: [Mn(5-Cl-sal2323)]2[ReCl6] (1) and [Mn(5-Br-sal2323)]2[ReCl6] (2). Their crystal structures and magnetic properties have been studied. These isostructural two-component ionic compounds show a thermally induced spin transition at high temperature associated with the cationic subsystem and a field-induced slow magnetic relaxation of magnetization at cryogenic temperature, associated with the anionic subsystem. The compounds are the first examples of the coexistence of spin crossover and field-induced slow magnetic relaxation in the family of known [MnIII(sal2323)] cationic complexes with various counterions.

Creation of spin switching in graphene oxide-based hybrid film materials with an anionic Fe(III) 5Cl-salicyaldehyde-thiosemicarbazone complex.

The present article describes the synthesis of hybrid composite film materials formed during the self-assembly process through non-covalent interactions of graphene oxide (GO) nanosheets with salt 1, represented by an anionic spin-crossover complex [FeIII(5Cl-thsa)2]- (5Cl-thsa - 5-chlorosalicylaldehyde thiosemicarbazone) and the organic tetraethylammonium cation [Et4N]+. The insertion of the salt 1 molecules into the interlayer space of GO nanosheets with the subsequent formation of a hybrid material GO-1 was observed. The film of the hybrid material GO-1 was characterized by scanning electron and confocal laser microscopy, EDX and XPS analysis, IR, Raman and 57Fe Mössbauer spectroscopy, dc magnetic measurements, and powder X-ray diffraction. Comparison of the magnetic properties of salt 1 and a film of the hybrid material GO-1 demonstrated a significant influence of the GO nanosheets matrix on the completeness of spin transition and showed a slight shift of the hysteresis loop by 1 K in the temperature range of 200-230 K. DFT calculations showed an important role of the organic cation [Et4N]+ in the process of adsorption of the spin-crossover anion [FeIII(5Cl-thsa)2]- on the GO nanosheet surface.

Hydrophobization of Reduced Graphene Oxide Aerogel Using Soy Wax to Improve Sorption Properties.

A special technique has been developed for producing a composite aerogel which consists of graphene oxide and soy wax (GO/wax). The reduction of graphene oxide was carried out by the stepwise heating of this aerogel to 250 °C. The aerogel obtained in the process of the stepwise thermal treatment of rGO/wax was studied by IR and Raman spectroscopy, scanning electron microscopy, and thermogravimetry. The heat treatment led to an increase in the wax fraction accompanied by an increase in the contact angle of the rGO/wax aerogel surface from 136.2 °C to 142.4 °C. The SEM analysis has shown that the spatial structure of the aerogel was formed by sheets of graphene oxide, while the wax formed rather large (200-1000 nm) clumps in the folds of graphene oxide sheets and small (several nm) deposits on the flat surface of the sheets. The sorption properties of the rGO/wax aerogel were studied with respect to eight solvent, oil, and petroleum products, and it was found that dichlorobenzene (85.8 g/g) and hexane (41.9 g/g) had the maximum and minimum sorption capacities, respectively. In the case of oil and petroleum products, the indicators were in the range of 52-63 g/g. The rGO/wax aerogel was found to be highly resistant to sorption-desorption cycles. The cyclic tests also revealed a swelling effect that occurred differently for different parts of the aerogel.

Direct Nanoscale Visualization of the Electric-Field-Induced Aging Dynamics of MAPbI3 Thin Films.

Perovskite solar cells represent the most attractive emerging photovoltaic technology, but their practical implementation is limited by solar cell devices' low levels of operational stability. The electric field represents one of the key stress factors leading to the fast degradation of perovskite solar cells. To mitigate this issue, one must gain a deep mechanistic understanding of the perovskite aging pathways associated with the action of the electric field. Since degradation processes are spatially heterogeneous, the behaviors of perovskite films under an applied electric field should be visualized with nanoscale resolution. Herein, we report a direct nanoscale visualization of methylammonium (MA+) cation dynamics in methylammonium lead iodide (MAPbI3) films during field-induced degradation, using infrared scattering-type scanning near-field microscopy (IR s-SNOM). The obtained data reveal that the major aging pathways are related to the anodic oxidation of I- and the cathodic reduction of MA+, which finally result in the depletion of organic species in the channel of the device and the formation of Pb. This conclusion was supported by a set of complementary techniques such as time-of-flight secondary ion mass spectrometry (ToF-SIMS), photoluminescence (PL) microscopy, scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX) microanalysis. The obtained results demonstrate that IR s-SNOM represents a powerful technique for studying the spatially resolved field-induced degradation dynamics of hybrid perovskite absorbers and the identification of more promising materials resistant to the electric field.