Solvent-Controlled Condensation of [Mo₂ O₅ (PTC4A)₂ ]^6- Metalloligand in Stepwise Assembly of Hexagonal and...

Stepwise assembly starting from a preassembled metalloligand is a promising approach to obtain otherwise unattainable silver nanoclusters, but hard to be intrinsically identified due to the lack of convincing evidence to justify such a process. Herein, hexagonal and rectangular Ag₁₈ nanoclusters are constructed from the [Mo₂ O₅ (PTC4A)₂ ]^6- (H₄ PTC4A=p-phenyl-thiacalix[4]arene) metalloligand through stepwise assembly. The formation of the metalloligand is confirmed by electrospray ionization mass spectrometry, then assembled with silver ions to form two geometrically different Ag₁₈ nanoclusters in different solvents. The cyclization from the metalloligand to [(Mo₂ O₅ PTC4A)₆ ]^12- can be realized without alcohols and otherwise blocked by them. The installation of this metalloligand not only provides comprehensive understanding of how the solvents regulate the silver nanocluster structures, but also brings new insights for the controllable ligand metallization and subsequent condensation.