High-nuclearity lanthaide-hydroxo complexes were prepared via limited hydrolysis of lanthanides using α-amino acids or EDTA as supporting ligands. These novel substances, synthesized under physiological or even higher-pH conditions, exist as tetranuclear cuboid [Ln~4(μ~3-OH)~4]^8^+ core-containing clusters. With appropriate halide templates, "whell-like" supramolecular structures composed of four or five vertex-sharing [Ln~4(μ~3-OH)~4]^8^+ units are formed. The face-capped octahedral [Ln~6(μ~6-O)(μ~3-OH)~8]^8^+] cluster centering on an interstitial μ~6-O ligand is another stable form of lanthanide-hydroxo complexes and can be self-assembled via direct hydrolysis of lanthanide nitrates and perchlorates. The significant influence of pH conditions on lanthanide coordination chemistry is further illustrated by a new paradigmatic lanthanide- EDTA chemistry, wherein unprecedented multinuclear Ln-EDTA cluster complexes are realized.

Key words: LANTHANIDE SERIES COMPOUNDS, COMPLEX COMPOUNDS, AMINO ACID, MARTIX EFFECTS, HYDROLYSIS, CUBANE