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Gigantic coordination molecules assembled from a large number of metal ions and organic ligands are structurally and functionally challenging to characterize. Here we show that a heterometallic clu...

An air-stable dysprosium(iii) complex, [C(NH2)3]4[DyF(piv)4](piv)2 (piv = pivalate), with a terminal fluoride ligand protected by forming extensive hydrogen bonds with peripheral guanidiniums has been isolated. Though the magnetic data failed to determine the energy barrier for the magnetic reversal (Ueff) accurately, the fine emission spectrum of the 4F9/2→6H15/2 transition at 4.2 K and ab initio calculations reveal that the Ueff is about 376(20) K, which is among the highest for high-coordinate (coordination numbers ≥ 9) lanthanide mononuclear magnets.

We report here that energy migration during luminescence can be extremely minimized by caging the fluorescent centers in a molecular cluster of [Tb6(μ3-F)8(piv)10(Hpiv)4DMF]·xDMF·yH2O 1. Experimental and theoretical simulations reveal that bonding terbium with fluoride is the key to reducing the non-radiative multi-phonon relaxation processes, which is disparate to the common hydroxy-based lanthanide clusters.

The asymmetric unit of the title compound, C18H15N63+·3Cl−·2.5H2O, contains two independent (1,3,5-triazine-2,4,6-triyl)tripyridinium cations. Both cations are approximately planar, the r.m.s. deviations of fitted non-H atoms being 0.045 and 0.051 Å. In the crystal, extensive O—H...Cl, O—H...O, N—H...Cl and N—H...O hydrogen bonds and weak C—H...Cl and C—H...O interactions link the organic cations, Cl−anions and water molecules into a three-dimensional supramolecular architecture. π–π stacking between the pyridine rings of adjacent cations is also observed, the centroid-to-centroid distance being 3.7578 (8) Å.