Ligand-Dependent Luminescence Properties of Lanthanide-Titanium Oxo Clusters.

A series of lanthanide-titanium oxo clusters (LnTOCs), LnTi-Ac, LnTi--Toluic, and LnTi-Anthra (Ln = Eu and Tb), were prepared based on acetic acid (HAc), -toluic acid (Hp-Toluic), and anthracene-9-carboxylic acid (HAnthra). Crystal structural analysis showed that these clusters possess the same metal topology framework, in which eight Ti ions form a cube and two Ln ions are located on the opposite faces of the cube. The luminescence investigation discovered that the EuTi-Ac displays the highest quantum yields with 15.

High-Nuclearity Lanthanide-Titanium Oxo Clusters as Luminescent Molecular Thermometers with High Quantum Yields.

Three heterometallic lanthanide-titanium oxo clusters (LnTOCs) formulated as EuTi(μ-O)(tbba)(acac) (EuTi, 1, Hacac = acetylacetone), EuTi(μ-O)(tbba)(Htbba)(THF) (EuTi, 2), and EuTi(μ-O)(Ac)(tbba)(HO)(THF)(Htbba) (EuTi, 3) were prepared through the reactions of 4-tert-butylbenzoate (Htbba), rare-earth salts, and Ti(OPr). The solution luminescence investigation discovered a size-dependent quantum yield phenomenon in solution. A solid-state luminescence study showed that these three LnTOCs display temperature-dependent photoluminescent properties.

Three Giant Lanthanide Clusters Ln (Ln = Gd, Tb, and Eu) Featuring A Double-Cage Structure.

Three homometallic high-nuclearity clusters, formulated as [(CO)@Ln(LH)(CHCOO)(CO)(μ-OH)(μ-HO)(HO)]·(ClO)·(HO) (abbreviated as Ln, Ln = Gd (1); Tb (2); Eu (3), LH = 1,2,3-cyclohexanetriol) and featuring a double cage-like structure, were obtained through the reaction of 1,2,3-cyclohexanetriol, acetate ligand, and Ln(ClO). The largest odd-numbered lanthanide cluster Gd exhibits an entropy change (-ΔS) of 38.7 J kg K.