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Pb[PtBi 6 I 12 ] – Infinite Chains of Heavy Atom Clusters
Author(s) -
Herz Maria A.,
Knies Maximilian,
Finzel Kati,
Ruck Michael
Publication year - 2021
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.202000336
Subject(s) - octahedron , crystallography , iodide , trigonal crystal system , bismuth , cluster (spacecraft) , chemistry , band gap , atom (system on chip) , lattice (music) , crystal structure , materials science , inorganic chemistry , physics , condensed matter physics , organic chemistry , computer science , acoustics , programming language , embedded system
Reaction of Bi with Pb, Pt and BiI 3 above 330 °C yielded shiny, black, air insensitive crystals of the subiodide Pb[PtBi 6 I 12 ]. Pb[PtBi 6 I 12 ] crystallizes in the rhombohedral space group R 3 with lattice parameters a = 1585.39(5) pm and c = 1098.77(3) pm at room temperature. The compound consists of cuboctahedral [PtBi 6 I 12 ] 2– clusters and Pb 2+ cations in octahedral coordination between trigonal faces of two cuboctahedra, which concatenate them into linear chains. Six weaker Bi ··· I inter‐cluster bridges per cluster connect the chains. The structure can be interpreted as a superstructure of the NaCl structure type, with iodide and platinum(–II) as anions and bismuth(II) and lead(II) as cations, leaving 18 out of 39 cation positions unoccupied. The arrangement of the cuboctahedral clusters follows the motif of a body‐centered cubic packing. Pb[PtBi 6 I 12 ] is a semiconductor with a measured bandgap of 0.69 eV. Full‐relativistic DFT calculations indicate a topologically trivial bandgap of 0.58 eV.