New Environment for a Two-Dimensional Topological Insulator with Hexagonal Channels Hosting Diiodido-bismuthate(I) Anions in a Singlet State

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• 作者：Bertold Rasche ; Wouter Van den Broek ; Michael Ruck
• 刊名：Chemistry of Materials
• 出版年：2016
• 出版时间：January 26, 2016
• 年：2016
• 卷：28
• 期：2
• 页码：665-672
• 全文大小：390K
• ISSN：1520-5002

文摘

A honeycomb layer of transition metal-centered bismuth cubes has attracted attention as part of the weak topological insulator (TI) Bi₁₄Rh₃I₉. The intermetallic layer itself is a two-dimensional TI and has been found in Bi₁₃Pt₃I₇ and Bi₁₂Pt₃I₅, as well as in the new material Bi₃₈Pt₉I₁₄, yet with different stacking sequences and types of insulating spacer layers in all cases. The arrangements strongly influence the electronic situation, especially the coupling between the TI layers. X-ray diffraction and electron microscopy show that in Bi₃₈Pt₉I₁₄ the intermetallic layers are exclusively separated by single layers of iodide ions. The eclipsed stacking of the honeycomb layers results in hexagonal channels. These host hitherto unknown linear [BiI₂]^? anions with bismuth atoms in the uncommon +I oxidation state. Quantum chemical calculations as well as magnetic susceptibility data indicate a singlet state stabilized by strong spin–orbit coupling. Bi₃₈Pt₉I₁₄ is a semiconductor with a very narrow energy gap, as resistivity measurements show. The nontrivial topological invariants of the electronic bands at the Fermi energy and the coupling of TI layers throughout the crystal suggest even a strong TI.