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Abstract:
Ordered single-crystals of the metallic subiodide Bi13Pt3I7 were grown
and treated with n-butyllithium. At 45 degrees C, complete
pseudomorphosis to Bi12Pt3I5 was achieved within two days. The new
compound is air-stable and contains the same
(2)(infinity)[Bi12Pt3I5](n+) honeycomb nets and iodide layers as the
starting material Bi13Pt3I7, but does not include
(2)(infinity)[Bi12Pt3I5](n+) iodidobismuthate strands. Electron
microscopy and X-ray diffraction studies of solid intermediates
visualize the process of the topochemical crystal-to-crystal
transfor-mation. 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.
