Acid–Base‐Triggered Structural Transformation of a Polyoxometalate Core Inside a Dodecahedrane‐like Silver Thiolate Shell

Abstract

Self-assembly of metavanadate and organosilver(I) salts leads to an ovel dodecahedrane-like [Ag 30 ( t BuS) 20 ] 10+ silver(I) thiolate nanocage that tightly wraps an unusual C 2h polyoxovanadate anion. The polyoxovanadate core undergoes transformation to aD 3d configuration upon acidification, and reverts back to its original C 2h structure upon addition of base. Chromism was observed for the silver(I) thiolate cluster during the configurational change of the central polyoxovanadate core;the color of the solution changes reversibly from green to dark yellow.This work represents the first reported example of chromic polyoxometalate-templated silver(I) thiolate shells that respond to external acid-base stimuli. It also represents an important advance in providing crystallographic proof that structural transformations occur in an anoscale core-shell cluster.

A Keplerian Ag90 nest of Platonic and Archimedean polyhedra in different symmetry groups

“…Structures of SD/Ag90a and SD/Ag90b. With a combination of anion-template and geometrical-polyhedron strategies [31][32][33][34][35][36][37] and with careful choice of organic ligands ( t BuSH and PhPO 3 H 2 ) and anion templates (S 2− and PO 4 3− ), we one-pot synthesized Ag 90 nanoclusters under the solvothermal condition as dark brown or red rhombic crystals, depending on the polymorphs. They are stable under ambient conditions because the bulk sample of them can keep the color and morphology unchanged for at least one month.…”

Trapping an octahedral Ag6 kernel in a seven-fold symmetric Ag56 nanowheel

“…Recent work showed the encapsulation of POMs into silver-thiolate/alkynyl clusters could effectively direct the nuclearity and geometry of the final products depending on the size and shape of the POMs 32 – 38 . Moreover, POMs usually isomerize or transform to other forms different from their original compositions and structures when enwrapped into the silver clusters 39 , which should be controlled by the pH of the assembly environment and influenced by polarity of solvents 40 . On the other hand, solvents such as DMF ( N , N -Dimethylformamide) contain aldehyde group that not only could endow electrons from O atom to form coordination bond with metal centre, but also has the ability to reduce Ag(I) to Ag(0) 41 , which favours the formation of type-I silver clusters.…”

A hierarchically assembled 88-nuclei silver-thiacalix[4]arene nanocluster

“…Except for the ligand selection, oxoanion template plays another dominant role in constructing silver nanoclusters due to the strong directional effect arising from Ag-O interaction. [36][37][38][39][40][41] In most cases of anion-templated assembly, oxoanions commonly exert the global effect that means the metal ions aggregate around them in a roughly chaotic fashion without any precedence. As we know, shuttlecock-like {M 4 (TC4A)} (M = Mn, Fe, Co, and Ni) is a very common secondary building unit (SBU) in TC4A 4− -capped metal nanoclusters; 42 however, we do not know what is the SBU if metal is switched to silver in the presence of the anion template.…”