Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 134, Issue 2, Pages 1181-1191Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja209226b
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Funding
- German Science Foundation (DFG)
- Association of the Chemical Industry(FCI)
- University of Bordeaux
- Region Aquitaine
- GIS Advanced Materials in Aquitaine (COMET)
- CNRS
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Two K([2.2.2]crypt) salts of lanthanide-doped semimetal clusters were prepared, both of which contain at the same time two types of ternary intermetalloid anions, [Ln@Sn7Bi7](4-) and [Ln@Sn4Bi9](4-), in 0.70:0.30 (Ln = La) or 0.39:0.61 (Ln = Ce) ratios. The cluster shells represent nondeltahedral, fullerane-type arrangements of 14 or 13 main group metal atoms that embed the Ln(3+) cations. The assignment of formal +III oxidation states for the Ln sites was confirmed by means of magnetic measurements that reveal a diamagnetic La(III) compound and a paramagnetic Ce(III) analogue. Whereas the cluster anions with a 14-atomic main-group metal cage represent the second examples in addition to a related Eu(II) cluster published just recently, the 13-atomic cages exhibit a yet unprecedented enneahedral topology. In contrast to the larger cages, which accord to the Zintl-Klemm-Busmann electron number-structure correlation, the smaller clusters require a more profound interpretation of the bonding situation. Quantum chemical investigations served to shed light on these unusual complexes and showed significant narrowing of the HOMO-LUMO gap upon incorporation of Ce3+ within the semimetal cages.
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