Different mechanisms for lanthanide(III) sensitization and Yb-field-induced single-molecule magnet behaviour in a series of pentagonal bipyramidal and octahedral lanthanide complexes with axial phosphine oxide ligands.

Seven mononuclear lanthanide complexes have been isolated and structurally characterised. Four of them are cationic, whose charges are balanced by chloride counteranions, and exhibit pentagonal bipyramidal coordination geometry, whereas the rest of them are neutral and display octahedral coordination environment. In all cases, the coordination sphere of the Ln ions consists of two di(1-adamantyl)benzylphosphine oxide ligands in axial positions, whereas in the equatorial plane the former contains a chloride and four water molecules and the latter a solvent molecule and three chloride ligands. We report a detailed photophysical investigation, including time-dependent density functional theory (TD-DFT) calculations and intramolecular energy transfer (IET) analysis, which reveals two distinct lanthanide sensitization mechanisms. Compound-specific energy transfer pathways occur through either the S or T states, as supported by calculated IET rates and resonance with lanthanide acceptor transitions. In addition, dc and ac magnetic properties were measured on complexes 1 and 2, showing that compound 1 behaves as a bi-functional compound, exhibiting field-induced single molecule magnet behaviour together with Yb-centred NIR luminescence. The relaxation of the magnetization in this pentagonal bipyramidal complex takes place through Raman and direct processes, as supported by calculations.