Abstract
The mixed metal hexathiohypodiphosphate Mn x Cd 1− x PS 3 (0 < x ⩽ 1) system and its two new series of related intercalates based on tetraethylammonium (Et 4N +) (Series A) and 2,2′-bipyridine (bipy) (Series B) have been synthesized and characterized by X-ray powder diffraction, infrared spectroscopy and element analysis, respectively. All Mn x Cd 1− x PS 3 ( x = 0.18, 0.52, 0.82 and 1.0) compounds have the similar structure to pure MnPS 3. In series A, the lattice expansion (Δ d) of intercalates (Mn 0.86PS 3(Et 4N) 0.28, A1; Mn 0.68Cd 0.17PS 3(Et 4N) 0.30, A2; Mn 0.36Cd 0.47PS 3(Et 4N) 0.34, A3; Mn 0.05Cd 0.79PS 3(Et 4N) 0.32, A4) is about 5.0 Å, and the charge balance of insertion of Et 4N + cation into layered space of the host are maintained by the departure of intralayered Mn 2+ ions of the host. However, in series B the intralayered Cd 2+ ions are removed by the insertion of 2,2′-bipyridine into layered space of the host, and the lattice expansion (Δ d) of the intercalates (Mn 0.77PS 3(bipy) 0.44, B1; Mn 0.73Cd 0.05PS 3(bipy) 0.44, B2; Mn 0.43Cd 0.34PS 3(bipy) 0.46, B3; Mn 0.18Cd 0.54PS 3(bipy) 0.56, B4) is about 9.0 Å. The magnetic properties are studied with SQUID. It is found that the magnetic properties of Mn x Cd 1− x PS 3 system are changed from antiferromagnetism to paramagnetism with the increase of Cd 2+ ions. In Series A and B, the intercalates ( A1– 2 and B1– 2) that have less Cd 2+ ions exhibit bulk spontaneous magnetization at low-temperature. And the intercalates ( A3– 4 and B3– 4), which have more Cd 2+ ions, only exhibit paramagnetism. Obviously, the existence of diamagnetic Cd 2+ ions dilutes the magnetic interaction of Mn 2+ ions in Mn x Cd 1− x PS 3 system and its related intercalates. It is also found that either the departure of intralayered Mn 2+ or Cd 2+ ions from the host can induce the ferromagnetization at low-temperature when the content of Mn 2+ ions is over 0.70.
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