Design of High-Temperature Syntheses on the Example of the Heavy-Atom Cluster Compound Sn[PtBi6I12]

Publikation: Beitrag in FachzeitschriftForschungsartikelBeigetragenBegutachtung

Abstract

Investigations into potential topological materials yielded the new subiodide Sn[PtBi6I12]. The combination of thermal analyses with phase analyses of the products of isothermal ex situ syntheses allowed the establishment of a complex high-temperature synthesis protocol for the crystal growth of the target phase despite the lack of knowledge of the quaternary phase diagram. A special challenge was to prevent the formation of competing compounds of the solid solution series (Bi2xSn1–3x)[PtBi6I12] with x≠0. Sn[PtBi6I12] crystallizes, isostructural to Pb[PtBi6I12], in the rhombohedral space group R (Formula presented.) with lattice parameters a=1583.2(2) pm and c=1089.70(10) pm. The compound consists of cuboctahedral [PtBi6I12]2− clusters and Sn2+ cations in an octahedral coordination between the trigonal faces of two cluster units, thereby concatenating them into infinite linear chains. The chains are connected via Bi...I inter-cluster bridges, creating a high-entropy variant of the NaCl structure type. Sn[PtBi6I12] is a semiconductor with an experimental bandgap of 0.8(1) eV. Fully relativistic density functional theory calculations including an implementation of the bifunctional formalism for the exchange energy indicate a topologically trivial bandgap of 0.81 eV between bands that are dominated by contributions of bismuth and iodine.

Details

OriginalspracheEnglisch
Aufsatznummere202200080
FachzeitschriftZeitschrift fur Anorganische und Allgemeine Chemie
Jahrgang648
Ausgabenummer17
PublikationsstatusVeröffentlicht - 13 Sept. 2022
Peer-Review-StatusJa

Externe IDs

Scopus 85128086041
Mendeley 8a43f0cf-caf1-39b6-b1bf-94f7af90a232
ORCID /0000-0002-2391-6025/work/142250224

Schlagworte

DFG-Fachsystematik nach Fachkollegium

Fächergruppen, Lehr- und Forschungsbereiche, Fachgebiete nach Destatis

ASJC Scopus Sachgebiete

Schlagwörter

  • bifunctional formalism, bismuth, cluster compounds, crystal growth, spin-orbit coupling