Dynamic disorder of Bi82+ clusters in the plastic phase (Bi8)3Bi[InI4]9
Publikation: Beitrag in Fachzeitschrift › Forschungsartikel › Beigetragen › Begutachtung
Beitragende
Abstract
Black, air-insensitive crystals of the bismuth-rich tetra-iodido- indate(III) (Bi8)3Bi[InI4]9 have been prepared from melts of the contributing elements. X-ray diffraction on a single crystal at 293 K and 220 K revealed a cubic structure with [InL 4]- tetrahedra, isolated Bi3+ ions and rotationally disordered Bi82+ square anti-prisms ace group Fm3̄c; a = 20.162(2) Å at T = 293(1)]. The principal arrangement of the complex ions corresponds to the AuCu3 type. The small bulk modulus Bo = 12(1) GPa and its large pressure derivative B o' = 11(1) as well as the low Debye temperature θD = 52 K are in accordance with a plastic behavior. Cooling below 148(1) K induces the first order transition into an ordered phase with 0.43 % higher density but much larger unit cell and lower crystallographic point group. The transition enthalpy AH ≈ 3.8 kJ-mol-1 and transition entropy AS ≈ 3 R were determined from specific heat data. A similar reversible phase transition into a lower symmetric structure is observed at a pressure of approximately 5 GPa. (Bi8)3Bi[InI4]9 is a diamagnetic semiconductor.
Details
Originalsprache | Englisch |
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Seiten (von - bis) | 1030-1035 |
Seitenumfang | 6 |
Fachzeitschrift | Zeitschrift fur Anorganische und Allgemeine Chemie |
Jahrgang | 635 |
Ausgabenummer | 6-7 |
Publikationsstatus | Veröffentlicht - Mai 2009 |
Peer-Review-Status | Ja |
Externe IDs
ORCID | /0000-0002-2391-6025/work/159171902 |
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Schlagworte
ASJC Scopus Sachgebiete
Schlagwörter
- Bismuth, Cluster compounds, Order disorder transition, Plastic phase, Polycations