Size Selectivity in Heterolanthanide Molecular Complexes with a Ditopic Ligand

The similar reactivity of lanthanides generally leads to statistically populated polynuclear complexes, making the rational design of ordered hetero‐lanthanide compounds extremely challenging. Here we report on the site selectivity in hetero‐lanthanide tetranuclear complexes afforded by the relatively simple ditopic pyterpyNO ligand (4’‐(4‐pyridil)‐2,2’:6’,2”‐terpyridine N‐oxide). The sequential room temperature reaction of RE(2)(tta)(6)(pyterpyNO)(2) (where RE=Y, (1); Eu, (2), Dy, (3) Htta=2‐thenoyltrifluoroacetone) with La(tta)(3)dme (dme=dimethoxyethane) yielded Y(2)La(2)(tta)(12)(pyterpyNO)(2) (4), Dy(2)La(2)(tta)(12)(pyterpyNO)(2) (5) and Eu(2)La(2)(tta)(12)(pyterpyNO)(2) (6). Single crystals X‐ray diffraction studies showed that 4, 5 and 6 are isostructural, featuring a tetranuclear structure with two different metal coordination sites with coordination numbers 8 (CN8) and 9 (CN9). The two smaller cations are mainly bridged by the O‐donor atoms of the NO groups of two pyterpyNO ligands (CN8), while the larger lanthanum centres are bound by a terpyridine unit (CN9). Size selectivity has been studied with structural and magnetic studies in the solid state and through (19)F NMR and photoluminescence studies in solution, showing a direct dependence on the difference of ionic radii of the ions and yielding a 91 % selectivity for 4. Furthermore, (19)F NMR, X‐ray and PL studies pointed out that the nature of the product is independent from the synthetic route for compound Eu(2)Y(2)(tta)(12)(pyterpyNO)(2) (7), keeping the ion selectivity also for a self‐assembly reaction. Unexpectedly, these studies have evidenced that selectivity is not exclusively governed by electrostatic interactions related to size dimensions.