Hydrolysis-Promoted Building Block Assembly: Structure Transformation from Y12 Wheel and Y34 Ship to Y60 Cage.

Accurately controlling the hydrolysis of metal ions can not only yield the desired structure of metal hydroxide clusters but also provide a deeper understanding of the formation process of natural hydroxide minerals. However, the capture of hydrolysis intermediates remains a significant challenge, and metal hydroxide clusters are mainly obtained by employing adventitious hydrolysis. In this study, we realized a hierarchical building block assembly from Y3+ ions to large Y12, Y34, and Y60 clusters by controlling the hydrolysis process of lanthanide ions under different pH conditions. Single-crystal structural analysis showed that the Y12 wheel, Y34 ship, and Y60 sodalite cage contain 4, 12, and 24 cubane-like [Y4(µ3-OH)4]8+ units, respectively. The structure of the Y60 cluster can be attributed to two Y34 clusters or six Y12 clusters linked by vertices. These clusters can be synthesized through the hydrolysis of Y3+ under different pH conditions, and Y60 can be prepared from the obtained Y12 or Y34 crystals by the simple addition of Y3+ ions. The capture and conversion of the intermediates of lanthanide series hydroxide clusters, Y12 or Y34, during the assembly from Y3+ ions to Y60 can facilitate an understanding of the formation process of high-nuclearity lanthanide clusters.