| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 75978 | Microporous and Mesoporous Materials | 2008 | 8 Pages |
The mixed metal hexathiohypodiphosphate MnxCd1−xPS3 (0 < x ⩽ 1) system and its two new series of related intercalates based on tetraethylammonium (Et4N+) (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 MnxCd1−xPS3 (x = 0.18, 0.52, 0.82 and 1.0) compounds have the similar structure to pure MnPS3. In series A, the lattice expansion (Δd) of intercalates (Mn0.86PS3(Et4N)0.28, A1; Mn0.68Cd0.17PS3(Et4N)0.30, A2; Mn0.36Cd0.47PS3(Et4N)0.34, A3; Mn0.05Cd0.79PS3(Et4N)0.32, A4) is about 5.0 Å, and the charge balance of insertion of Et4N+ cation into layered space of the host are maintained by the departure of intralayered Mn2+ ions of the host. However, in series B the intralayered Cd2+ ions are removed by the insertion of 2,2′-bipyridine into layered space of the host, and the lattice expansion (Δd) of the intercalates (Mn0.77PS3(bipy)0.44, B1; Mn0.73Cd0.05PS3(bipy)0.44, B2; Mn0.43Cd0.34PS3(bipy)0.46, B3; Mn0.18Cd0.54PS3(bipy)0.56, B4) is about 9.0 Å. The magnetic properties are studied with SQUID. It is found that the magnetic properties of MnxCd1−xPS3 system are changed from antiferromagnetism to paramagnetism with the increase of Cd2+ ions. In Series A and B, the intercalates (A1–2 and B1–2) that have less Cd2+ ions exhibit bulk spontaneous magnetization at low-temperature. And the intercalates (A3–4 and B3–4), which have more Cd2+ ions, only exhibit paramagnetism. Obviously, the existence of diamagnetic Cd2+ ions dilutes the magnetic interaction of Mn2+ ions in MnxCd1−xPS3 system and its related intercalates. It is also found that either the departure of intralayered Mn2+ or Cd2+ ions from the host can induce the ferromagnetization at low-temperature when the content of Mn2+ ions is over 0.70.
