Visible-Light-Sensitized Near-Infrared Luminescence from Rare-Earth Complexes of the 9-Hydroxyphenalen-1-one Ligand

The unique absorption properties of the 9-hydroxyphenalen-1-one
(HPHN) ligand have been exploited to obtain visible-light-sensitizable rare-earth complexes in 1:3 and 1:4 metal-to-ligand
ratios. In both stoichiometries (1:3, tris, Ln(PHN)3; 1:4, tetrakis,
A[Ln(PHN)4], with Ln being a trivalent rare-earth ion and A being
a monovalent cation), the complexes of Nd(III), Er(III), and Yb(III)
show typical near-infrared luminescence upon excitation with visible
light with wavelengths up to 475 nm. The X-ray crystal structures
of the tris complexes show solvent coordination to the central rare-earth ion, whereas in the tetrakis complexes, the four PHN- ligands
form a protective shield around the central ion, preventing small
solvent molecules from coordinating to the rare-earth ion, at least
in the solid state.