Site-Selective Lanthanide Doping in a Nonanuclear Yttrium(III) Cluster Revealed by Crystal Structures and Luminescence Spectra

A series of lanthanide-doped nonanuclear yttrium(III) clusters with general formulas (Y(9-x)Ln(x))(acac)(16)(mu(3)-OH)(8)-(mu(4)-O)(mu(4)-OH) (Ln = Pr, Eu, Tb, Dy, and Yb) were synthesized. Characterization by single-crystal X-ray diffraction allowed for analysis of relative populations of yttrium (Z = 39) and dopant trivalent lanthanide (Z = 59-70) at every crystallographic metal position. Nonuniform distribution of ions along the three different sites seems to be correlated to the site volume and the ratio of ionic radii. In support, luminescence spectra of europium(III)-doped nonanuclear clusters were measured over a wide range of dopant concentrations. Emission intensities of peaks characteristic of specific sites correlate well with the site population determined through X-ray diffraction.