Coordination-directed self-assembly has become a well-established technique for the construction of functional supramolecular structures. In contrast to the most often exploited transition metals, trivalent lanthanides Ln(III) have been less utilized in the design of polynuclear self-assembled structures despite the wealth of stimulating applications of these elements. In particular, stereochemical control in the assembly of lanthanide chiral cage compounds is not easy to achieve in view of the usually large lability of the Ln(III) ions. We report here the first examples of stereoselective self-assembly of chiral luminescent europium coordination tetrahedral cages and their intriguing self-sorting behavior. Two pairs of R and S ligands are designed on the basis of the pyridine-2,6-dicarboxamide coordination unit, bis(tridentate) L1 and tris(tridentate) L2. Corresponding chiral Eu4(L1)6 and Eu4(L2)4 topological tetrahedral cages are independently assembled via edge- and face-capping design strategies, respectively. The chirality of the ligand is transferred during the self-assembly process to give either Δ or Λ metal stereochemistry. The self-assembled cages are characterized by NMR, high-resolution ESI-TOF-MS, and in one case by X-ray crystallography. Strict control of stereoselectivity is confirmed by CD spectroscopy and NMR enantiomeric differentiation experiments. Narcissistic self-sorting is observed in the self-assembly process when two differently shaped ligands L1 and L2 are mixed. More impressively, distinct self-sorting behavior between Eu4(L1)6 and Eu4(L2)4 coordination cages is observed for the first time when racemic mixtures of ligands are used. We envisage that chiral luminescent lanthanide tetrahedral cages could be used in chiroptical probes\sensors and enantioselective catalysis.

Lanthanide-containing molecules have many potential applications in material science and biology, that is, luminescent sensing/labling, MRI, magnetic refrigeration, and catalysis among others. Coordination-directed self-assembly has shown great power in the designed construction of well-defined supramolecular systems. However, application of this strategy to the lanthanide edifices is challenging due to the complicated and greatly labile coordination numbers and geometries for lanthanides. Here we demonstrate a sensitive structural switching phenomenon during the stereocontrolled self-assembly of a group of LnL (Ln for lanthanides, L for organic ligands, and n = 1, 2, 4) compounds. Systematic variation of the offset distances between the two chelating arms on the bis(tridentate) ligands dictated the final outcomes of the lanthanide assembly, ranging from LnL helicates and LnL tetrahedra to LnL cubes. Remarkably, the borderline case leading to the formation of a mixture of the helicate and the tetrahedron was clearly revealed. Moreover, the concentration-dependent self-assembly of an unprecedented cubic LnL complex was also confirmed. The luminescent lanthanide cubes can serve as excellent turn-off sensors in explosives detection, featuring high selectivity and sensitivity toward picric acid. All complexes were confirmed by NMR, ESI-TOF-MS, and single crystal X-ray diffraction studies. Our results provide valuable design principles for the coordination self-assembly of multinuclear functional lanthanide architectures.

Lanthanide-containing functional complexes have found a variety of applications in materials science and biomedicine because of their unique electroptical and magnetic properties. However, the poor stability and solubility in water of multicomponent lanthanide organic assemblies significantly limit their practical applications. We report here a series of water-stable anionic Ln2n L3n -type (n = 2, 3, 4, and 5) lanthanide organic polyhedra (LOPs) constructed by deprotonation self-assembly of three fully conjugated ligands (H4L1 and H4L2a/b) featuring a 2,6-pyridine bitetrazolate chelating moiety. The outcomes of the LOPs formation reactions were found to be very sensitive toward the reaction conditions including base, metal source, solvents, and concentrations as characterized by a combination of NMR, high-resolution ESI–MS and X-ray crystallography. Ligands H4L2a/b manifested an excellent sensitization toward lanthanide ions (Ln = EuIII and TbIII), with high luminescent quantum yields for Tb8L2a 12 (Φ = 11.2% in water) and Eu8L2b 12 (Φ = 76.8% in DMSO) measured in polar solvents. Furthermore, due to the giant molecular weight and rigidity of the polyhedral skeleton, Gd8L2b 12 showed a very high longitudinal relaxivity (r 1) of 400.53 mM–1S–1. The performance of Gd8L2b 12 as potential magnetic resonance imaging contrast agents (CAs) in vivo was evaluated with much longer retention time in the tumor sites compared with the commercial GdIII-based CAs. Dual-modal imaging potential has also been demonstrated with the mixed Eu/Gd LOPs. Our results not only provide a new design route toward water-stable multinuclear lanthanide organic assemblies but also offer potential candidates of supramolecular-edifices for bioimaging and drug delivery.