Assembly of Hydrophobic Shells and Shields around Lanthanides

Luminescent lanthanide complexes have been developed, based on the assembly of bulky ligands around the lanthanide ion, to provide shell-type protection of the ion from coordinated solvent molecules. Aryl-functionalised imidodiphosphinate ligands (tpip and Metpip) provide a bidentate anionic site that leads to hexa-coordinate lanthanide complexes in which the aryl groups surround the ion. There are twelve phenyl groups around the lanthanide that act as "remote" (from the binding site) sensitisers for the metal ion. It is shown that these ligands are suitable for sensitising luminescence for all the lanthanides that emit in the visible range, namely, SmIII, EuIII, TbIII, DyIII. A "builtin" shield on the ligand is designed to provide a complete block of the approach of water to the lanthanide ion. The synthesis of the ligands and their lanthanides complexes as well as detailed photophysical studies of the complexes in solution and in the solid-state are presented.