Hydrolysis-Promoted Building Block Assembly: Structure Transformation from Wheel and Ship to 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 Y ions to large , , and clusters by controlling the hydrolysis process of lanthanide ions under different pH conditions. Single-crystal structural analysis showed that the wheel, ship, and sodalite cage contain 4, 12, and 24 cubane-like [Y(μ-OH)] units, respectively. The structure of the cluster can be attributed to two clusters or six clusters linked by vertices. These clusters can be synthesized through the hydrolysis of Y under different pH conditions, and can be prepared from the obtained or crystals by the simple addition of Y ions. The capture and conversion of the intermediates of lanthanide series hydroxide clusters, or , during the assembly from Y ions to can facilitate an understanding of the formation process of high-nuclearity lanthanide clusters.