Low-Temperature Topochemical Transformation of Bi₁₃Pt₃I₇ into the New Layered Honeycomb Metal Bi₁₂Pt₃I₅.

Kaiser, Martin; Rasche, Bertold; Isaeva, Anna; Ruck, Michael

Ordered single-crystals of the metallic subiodide Bi13Pt3I7 were grown and treated with n-butyllithium. At 45°C, complete pseudomorphosis to Bi12Pt3I5 was achieved within two days. The new compound is air-stable and contains the same ∞² [(PtBi8/2)3I]n honeycomb nets and iodide layers as the starting material Bi13Pt3I7, but does not include ∞¹[BiI2I4/2]- iodidobismuthate strands. Electron microscopy and X-ray diffraction studies of solid intermediates visualize the process of the topochemical crystal-to-crystal transformation. In the electronic band structures of Bi13Pt3I7 and Bi12Pt3I5, the vicinities of the Fermi levels are dominated by the intermetallic fragments. Upon the transformation of Bi13Pt3I7 into Bi12Pt3I5, the intermetallic part is oxidized and the Fermi level is lowered by 0.16 eV. Whereas in Bi13Pt3I7 the intermetallic layers do not interact across the iodidobismuthate spacers (two-dimensional metal), they couple in Bi12Pt3I5 and form a three-dimensional metal.

TOPOCHEMICAL reactions; BISMUTH; PLATINUM; HONEYCOMB structures; ELECTRONIC band structure; ELECTRON microscopy; X-ray diffraction

Chemistry - A European Journal, 2014, Vol 20, Issue 51, p17152

0947-6539

Academic Journal

10.1002/chem.201404789