Doped semimetal clusters: ternary, intermetalloid anions [Ln@Sn7Bi7]4- and [Ln@Sn4Bi9]4- (Ln = La, Ce) with adjustable magnetic properties

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@Sn(7)Bi(7)](4-) and Ln@Sn(4)Bi(9)](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 Ce(3+) within the semimetal cages.