Solvent‐Controlled Condensation of [Mo₂O₅(PTC4A)₂]⁶⁻ Metalloligand in Stepwise Assembly of Hexagonal and Rectangular Ag₁₈ Nanoclusters

Abstract

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 [Mo2O5(PTC4A)2]6− (H4PTC4A=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 [(Mo2O5PTC4A)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.

Synthesis and characterization of Ag(I) alkynyl nanoclusters utilizing Mo VI-anchored thiacalix[4]arene metalloligands: Application in electrocatalytic CO 2 reduction

“…This is the largest TC4A-based NC [45]. Furthermore, the incorporation of structure-directing additives, such as oxygen anions, polyoxometalates, and metalloligands, has shown immense potential in designing high-performance NCs [46][47][48][49][50][51][52][53][54][55]. Although the use of polyoxometalates has been advantageous in Ag NCs formation, achieving their rational design and preparation using metalloligands still requires further development.…”