The growth of single crystals of FeCl₃, through sublimation and from the melt, is presented alongside a thorough investigation of their magnetostructural properties through a combination of DC magnetization and AC magnetic susceptibility measurements, single crystal X-ray diffraction (SCXRD), neutron powder diffraction (NPD) and small-angle neutron scattering (SANS). A new chiral polymorph of FeCl₃ is identified, crystallizing in the non-centrosymmetric space group P3₁. NPD and SANS reveal that a weakly first-order magnetic phase transition occurs from a paramagnetic phase with significant short-range correlations to an antiferromagnetic phase at T_N = 8.6 K, best described by the magnetic propagation vector k = (1/2, 0, 1/3) which differs from the previously reported magnetic structure of the well-known centrosymmetric polymorph (space group R3̄). We show that disordered crystallographic models including a large number of stacking faults are required to accurately reproduce the scattering observed in NPD patterns, preventing full determination of the magnetic structure. The magnetic field and temperature-dependent behavior of the intensities of the k = (1/2, 0, 2/3) and (1/2, 0, 5/3) magnetic Bragg peaks measured by SANS suggest that a field-induced spin reorientation occurs at H = 40 kOe when H‖c-axis and at a significantly lower field of H ≈ 25 kOe when H⊥c-axis. Above these magnetic fields in both cases the spins lie predominantly in the basal plane. The long-range magnetic ordering and the field-induced transitions observed in the neutron scattering experiments coincide with anomalies observed in the magnetisation versus both temperature and applied field along the principal crystal directions.

We present a comprehensive investigation of the magnetic properties of stage-1 graphite intercalated FeCl3 using a combination of DC and AC magnetic susceptibility, thermoremanent magnetization, and field-dependent magnetization measurements. This van der Waals system, with a centrosymmetric honeycomb lattice, combines frustration and disorder, due to intercalation, and may be hosting topologically nontrivial magnetic phases. Our study identifies two magnetic phase transitions at Tf1≈4.2 K and at Tf2≈2.7 K. We find that the paramagnetic state, for T>Tf1, is dominated by short-range ferromagnetic correlations. These build up well above Tf1 and lead to a significant change in magnetic entropy, which reaches ΔSMPk=-5.52 J kg-1K-1 at 7 T. Between Tf1 and Tf2, we observe slow spin dynamics characteristic of a cluster glasslike state, whereas for T<Tf2, our results indicate the onset of a low-temperature long-range ordered state. The analysis of the experimental results leads to a complex phase diagram, which may serve as a reference for future investigations searching for topological nontrivial phases in this system.

We synthesize single crystals of a new 2,5-dimethylanilinium tin iodide organic-inorganic hybrid compound and 2,5-dimethylanilinium triiodide. Single-crystal X-ray diffraction reveals that the hybrid grows as a unique rhombohedral structure consisting of one-dimensional chains of SnI₆-octahedra that share corners and edges to build up a ribbon along the [111] direction. Notably, we find that hypophosphorous acid, H₃PO₂, is of central importance to the formation of this hybrid. In the absence of H₃PO₂, we synthesize 2,5-dimethylanilinium triiodide from the same starting compounds. We investigate the synthesis routes that drive the growth of these two compounds with distinct crystal structures, appearance and properties. Pulse-radiolysis time-resolved microwave conductivity measurements and density functional theory calculations reveal that both compounds have low charge carrier mobilities and very long lifetimes, consistent with their one-dimensional structural characteristics. Our findings give a better understanding of the relation between synthesis, crystal structures and charge carrier mobilities.

The alloys (GeTe)_x(AgSbTe₂)_100-x, commonly known as TAGS-x, are among the best performing p-type thermoelectric materials for the composition range 80 ≤ x ≤ 90 and in the temperature range 200-500 °C. They adopt a rhombohedrally distorted rocksalt structure at room temperature and are reported to undergo a reversible phase transition to a cubic structure at ∼250 °C. However, we show that, for the optimal x = 85 composition (TAGS-85), both the structural and thermoelectric properties are highly sensitive to the initial synthesis method employed. Single-phase rhombohedral samples exhibit the best thermoelectric properties but can only be obtained after an annealing step at 600 °C during initial cooling from the melt. Under faster cooling conditions, the samples obtained are inhomogeneous, containing multiple rhombohedral phases with a range of lattice parameters and exhibiting inferior thermoelectric properties. We also find that when the room-temperature rhombohedral phase is heated, an intermediate trigonal structure containing ordered cation vacancy layers is formed at ∼200 °C, driven by the spontaneous precipitation of argyrodite-type Ag₈GeTe₆ which alters the stoichiometry of the TAGS-85 matrix. The rhombohedral and trigonal phases of TAGS-85 coexist up to 380 °C, above which a single cubic phase is obtained and the Ag₈GeTe₆ precipitates redissolve into the matrix. On subsequent cooling a mixture of rhombohedral, trigonal, and Ag₈GeTe₆ phases is again obtained. Initially single-phase samples exhibit thermoelectric power factors of up to 0.0035 W m^-1 K^-2 at 500 °C, a value that is maintained on subsequent thermal cycling and which represents the highest power factor yet reported for undoped TAGS-85. Therefore, control over the structural homogeneity of TAGS-85 as demonstrated here is essential in order to optimize the thermoelectric performance.