Premium
Endohedrally Filled [Ni@Sn 9 ] 4− and [Co@Sn 9 ] 5− Clusters in the Neat Solids Na 12 Ni 1− x Sn 17 and K 13− x Co 1− x Sn 17 : Crystal Structure and 119 Sn Solid‐State NMR Spectroscopy
Author(s) -
Hlukhyy Viktor,
Stegmaier Saskia,
van Wüllen Leo,
Fässler Thomas F.
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.201402318
Subject(s) - crystallography , diamagnetism , alkali metal , laves phase , metal , valence (chemistry) , chemistry , materials science , intermetallic , physics , metallurgy , quantum mechanics , organic chemistry , alloy , magnetic field
Abstract A systematic approach to the formation of endohedrally filled atom clusters by a high‐temperature route instead of the more frequent multistep syntheses in solution is presented. Zintl phases Na 12 Ni 1− x Sn 17 and K 13− x Co 1− x Sn 17 , containing endohedrally filled intermetalloid clusters [Ni@Sn 9 ] 4− or [Co@Sn 9 ] 5− beside [Sn 4 ] 4− , are obtained from high‐temperature reactions. The arrangement of [Ni@Sn 9 ] 4− or [Co@Sn 9 ] 5− and [Sn 4 ] 4− clusters, which are present in the ratio 1:2, can be regarded as a hierarchical replacement variant of the hexagonal Laves phase MgZn 2 on the Mg and Zn positions, respectively. The alkali‐metal positions are considered for the first time in the hierarchical relationship, which leads to a comprehensive topological parallel and a better understanding of the composition of these compounds. The positions of the alkali‐metal atoms in the title compounds are related to the known inclusion of hydrogen atoms in the voids of Laves phases. The inclusion of Co atoms in the {Sn 9 } cages correlates strongly with the number of K vacancies in K 13− x Co 1− x Sn 17 and K 5− x Co 1− x Sn 9 , and consequently, all compounds correspond to diamagnetic valence compounds. Owing to their diamagnetism, K 13− x Co 1− x Sn 17 , and K 5− x Co 1− x Sn 9 , as well as the d‐block metal free binary compounds K 12 Sn 17 and K 4 Sn 9 , were characterized for the first time by 119 Sn solid‐state NMR spectroscopy.