This contribution investigates LnIII complexes formed with a small ditopic ligand, L1, and their structural, thermodynamic and photophysical properties. The spectrophotometric and NMR titrations evidence the triangular assemblies [Ln3(L1-H)3]6+ at stoichiometric conditions and their properties are discussed in relation to L2-containing analogues. In addition, the dinuclear species, [Ln2(L1-H)]5+, is observed with an excess of metal.