Giant Five-Shell Polyoxometalate Cages and the Single-Cluster-Based Nanowire Superstructures
Wenzhu Yang, Ya‐Jie Liu, Mingyue Wang, Xiaoya Wang, Xiaoya Wang, Qingda Liu, Linjie Lan, Panchao Yin, Cai‐Hong Zhan, Zhan‐Guo Jiang, Xun Wang, Xun Wang
Abstract
The preparation of polyoxometalate molecular cages has always been a long-term and challenging pursuit. In this work, we have successfully prepared two unprecedented giant heterogeneous POM-based purely inorganic molecular cages with O h symmetry, which contain the aggregation of M 6 (M = Ni, Co)-substituted trilacunary {PW 9 } and Mn-bridged {W 4 }. Sodium ions are used as templates to fill the cages. The polyanions of cages can be represented as {Na 6 (MnO 6 ) 12 (W 4 O 4 ) 12 [MnO 4 (OH 2 )] 6 (PW 9 Ni 6 O 49 H 15 ) 8 } and {Na 6 (MnO 6 ) 12 (W 4 O 4 ) 12 [MnO 4 (OH 2 )] 6 (PW 9 Co 6 O 49 H 15 ) 8 }. The entire structure can also be considered as a five-shell Na 6 @Mn 12 @{W 4 } 12 @Mn 6 @{PW 9 M 6 } 8 arrangement. The electrostatic effects of sodium ions within the cages enhance the stability of the structures, allowing them to maintain a monodisperse and stable state in aqueous solutions. Interestingly, the cages assemble into nanowires through electrostatic contact with the cationic CTA + ligand, demonstrating its flexible assembly capability at the single-cluster level. This giant POM inorganic molecular cage holds significant potential for application in the preparation of functional nanomaterials.