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Low‐Temperature Topochemical Transformation of Bi 13 Pt 3 I 7 into the New Layered Honeycomb Metal Bi 12 Pt 3 I 5
Author(s) -
Kaiser Martin,
Rasche Bertold,
Isaeva Anna,
Ruck Michael
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201404789
Subject(s) - intermetallic , crystallography , materials science , metal , iodide , fermi level , single crystal , superlattice , crystal structure , honeycomb , chemistry , electron , inorganic chemistry , metallurgy , physics , composite material , alloy , quantum mechanics , optoelectronics
Ordered single‐crystals of the metallic subiodide Bi 13 Pt 3 I 7 were grown and treated with n ‐butyllithium. At 45 °C, complete pseudomorphosis to Bi 12 Pt 3 I 5 was achieved within two days. The new compound is air‐stable and contains the same ${{{\hfill 2\atop \hfill \infty }}}$ [(PtBi 8/2 ) 3 I] n + honeycomb nets and iodide layers as the starting material Bi 13 Pt 3 I 7 , but does not include ${{{\hfill 1\atop \hfill \infty }}}$ [BiI 2 I 4/2 ] − 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 Bi 13 Pt 3 I 7 and Bi 12 Pt 3 I 5 , the vicinities of the Fermi levels are dominated by the intermetallic fragments. Upon the transformation of Bi 13 Pt 3 I 7 into Bi 12 Pt 3 I 5 , the intermetallic part is oxidized and the Fermi level is lowered by 0.16 eV. Whereas in Bi 13 Pt 3 I 7 the intermetallic layers do not interact across the iodidobismuthate spacers (two‐dimensional metal), they couple in Bi 12 Pt 3 I 5 and form a three‐dimensional metal.