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The Topochemical Pseudomorphosis of a Chloride into a Bismuthide
Author(s) -
Kaiser Martin,
Rasche Bertold,
Ruck Michael
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201309460
Subject(s) - intermetallic , isostructural , crystallography , materials science , bismuth , ionic bonding , chloride , crystal (programming language) , chemistry , ion , crystal structure , metallurgy , organic chemistry , alloy , computer science , programming language
The heterogeneous reaction of crystals of the novel intermetallic subhalide Bi 12 Rh 3 Cl 2 with a solution of n ‐butyllithium at 70 °C led to the complete topochemical exchange of chloride ions for bismuth atoms, that is, the transformation into the isostructural metastable intermetallic superconductor Bi 14 Rh 3 . The crystals underwent the reductive pseudomorphosis almost unchanged except some fissures perpendicular to the a ‐axis. Detailed inspections of the transformed crystals by electron microscopy indicated no volume defects that would indicate internal chemical reactions. Thus, extensive mass transport must have occurred through the seemingly dense crystal structure. An efficient transport mechanism, based on an unusual breathing mode of the three‐dimensional network formed by edge‐sharing [RhBi 8 ] cubes and antiprisms, is proposed. The replacement of ionic interaction in the chloride by metallic bonding in the binary intermetallic compound closes the pseudo gap in the density of states at the Fermi level. As a result, the rod‐packing of conducting, yet electrically isolated strands of [RhBi 8 ] cubes in Bi 12 Rh 3 Cl 2 turns into the three‐dimensional metal Bi 14 Rh 3 .