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Ionic‐Radius‐Driven Selection of the Main‐Group‐Metal Cage for Intermetalloid Clusters [Ln@Pb x Bi 14− x ] q − and [Ln@Pb y Bi 13− y ] q − ( x / q =7/4, 6/3; y / q =4/4, 3/3)
Author(s) -
Ababei Rodica,
Massa Werner,
Weinert Bastian,
Pollak Patrik,
Xie Xiulan,
Clérac Rodolphe,
Weigend Florian,
Dehnen Stefanie
Publication year - 2015
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.201404904
Subject(s) - ionic radius , crystallography , lanthanide , chemistry , ternary operation , paramagnetism , ion , ionic bonding , diamagnetism , analytical chemistry (journal) , physics , organic chemistry , chromatography , quantum mechanics , computer science , programming language , magnetic field
Reactions of the binary, pseudo‐homoatomic Zintl anion (Pb 2 Bi 2 ) 2− with Ln(C 5 Me 4 H) 3 (Ln=La, Ce, Nd, Gd, Sm, Tb) in the presence of [2.2.2]crypt in ethane‐1,2‐diamine/toluene yielded ten [K([2.2.2]crypt)] + salts of lanthanide‐doped semimetal clusters with 13 or 14 surface atoms. Single‐crystal X‐ray diffraction and energy‐dispersive X ‐ ray spectroscopy indicated the presence of the anions [Ln@Pb 6 Bi 8 ] 3− , [Ln@Pb 3 Bi 10 ] 3− , [Ln@Pb 7 Bi 7 ] 4− , or [Ln@Pb 4 Bi 9 ] 4− in single or double salts; the latter showed various ratios of the components in the solid state. The anions are the first ternary intermetalloid clusters comprising only elements of the sixth period of the periodic table, namely, Pb, Bi and lanthanides. This study, which was complemented by ESI mass spectrometry and 139 La NMR spectroscopy in solution, rationalizes a continuous development of the ratio of 13:14‐atom cages with the ionic radius of the embedded Ln 3+ ion, which seems to select the most suitable cage type. Quantum chemical investigations helped to analyze this situation in more detail and to explain the observed subtle influence of the atomic radii. Magnetic measurements confirmed that the embedded Ln 3+ ions keep their expected paramagnetic or diamagnetic nature.