We report magnetism of tetragonal β-Fe3Se4 nanoplates controllably synthesized by thermal decomposition at 603 K of inorganic–organic (β-Fe2Se3)4[Fe(tepa)] hybrid nanoplates (tepa = tetraethylenepentamine). (β-Fe2Se3)4[Fe(tepa)] hybrid precursor and β-Fe3Se4 nanoplates are in single crystal features as characterized by selected area electron diffraction. Rietveld refinements reveal that ordered inorganic–organic (β-Fe2Se3)4[Fe(tepa)] hybrid nanoplates are in a tetragonal layered crystal structure with a space group of I4cm (108) and room-temperature lattice parameters are a = 8.642(0) Å and c = 19.40(3) Å, while the as-synthetic tetragonal β-Fe3Se4 nanoplates have a layered crystal structure with the P4/nmm space group, and room-temperature lattice parameters are a = 3.775(8) Å and c = 5.514(5) Å. Magnetic measurements show the weak ferrimagnetism for (β-Fe2Se3)4[Fe(tepa)] hybrid nanoplates at room temperature, while the as-synthetic β-Fe3Se4 nanoplates are antiferromagnetic in a temperature range between 120 and 420 K but in a ferrimagnetic feature below ~120 K. The as-synthetic β-Fe3Se4 nanoplates are thermally instable, which are transformed to ferrimagnetic β-Fe3Se4 nanoplates by annealing at 623 K (a little higher than the synthetic temperature). There is an irreversible change from antiferromagnetism of the as-synthetic β-Fe3Se4 phase to the ferrimagnetism of the as-annealed β-Fe3Se4 phase in a temperature between 420 and 470 K. Above 470 K, the tetragonal β-Fe3Se4 phase transforms to monoclinic Fe3Se4 phase with a Curie temperature (TC) of ~330 K. This discovery highlights that crystal structure and magnetism of Fe-Se binary compounds are highly dependent on both their phase compositions and synthesis procedures.

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α″-Fe16N2 nanomaterials with a shape anisotropy for high coercivity performance are of interest in potential applications such as rare-earth-free permanent magnets, which are difficult to synthesize in situ anisotropic growth. Here, we develop a new and facile one-pot microemulsion method with Fe(CO)5 as the iron source and tetraethylenepentamine (TEPA) as the N/C source at low synthesis temperatures to fabricate carbon-coated tetragonal α″-Fe16N2 nanocones. Magnetocrystalline anisotropy energy is suggested as the driving force for the anisotropic growth of α″-Fe16N2@C nanocones because the easy magnetization direction of tetragonal α″-Fe16N2 nanocrystals is along the c axis. The α″-Fe16N2@C nanocones agglomerate to form a fan-like microstructure, in which the thin ends of nanocones direct to its center, due to the magnetostatic energy. The lengths of α″-Fe16N2@C nanocones are ~200 nm and the diameters vary from ~10 nm on one end to ~40 nm on the other end. Carbon shells with a thickness of 2–3 nm protect α″-Fe16N2 nanocones from oxidation in air atmosphere. The α″-Fe16N2@C nanocones synthesized at 433 K show a room-temperature saturation magnetization of 82.6 emu/g and a coercive force of 320 Oe.

Organic–inorganic hybrid materials built by inorganic and organic building units have attracted intensive interest in the past decades due to unique chemical and physical properties. However, rare organic–inorganic hybrid materials show excellent permanent magnetic properties. Here, we develop a facile chemical solution method to bottom-up synthesize a new hybrid (Fe2Se3)2[Fe(dien)2]0.9. This hybrid phase with the space group P21/c (14) possesses a rodlike shape with a diameter of 100–2000 nm and a length of 5–50 µm. The hybrid rods are ferrimagnetic with a Curie temperature (TC) of 11 K. They show a high coercivity (HC) of 4.67 kOe and a saturation magnetization (MS) of 13.5 emu/g at 2 K. Compared with orthorhombic (FeSe2)2Fe(dien)2, the excellent magnetic performance of the hybrid rods is ascribed to the monoclinic hybrid structure built by Fe(dien)2 complexes and Fe2Se3 double chains. Our study provides guidance for connecting inorganic fragments of FeSe2 single chains, Fe2Se3 double chains or β-Fe3Se4 layers with Fe(dien)2 complexes for organic–inorganic hybrid phases with varied crystal structures and magnetic properties.