Smart Transformation of a Polyhedral Oligomeric Silsesquioxane Shell Controlled by Thiolate Silver(I) Nanocluster Core in Cluster@Clusters Dendrimers

Using polyhedral oligomeric silsesquioxane (POSS) modified by a thiol group as a protected ligand, atom‐precise multi‐heteorocluster‐based dendrimers Ag12@POSS6 (1 a and 1 b) were assembled. Through the reactive −SH groups, six POSS shell ligands stabilize the central 12‐core silver(I) cluster by di...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-09, Vol.57 (39), p.12775-12779
Main Authors: Li, Si, Wang, Zhao‐Yang, Gao, Guang‐Gang, Li, Bing, Luo, Peng, Kong, Yu‐Jin, Liu, Hong, Zang, Shuang‐Quan
Format: Article
Language:English
Subjects:
Acetone
Clusters
Dendrimers
Hydrophobicity
Ligands
Nanoclusters
Polyhedral oligomeric silsesquioxane
polyhedral oligomeric silsesquioxanes
Protective coatings
Silver
solvent sensitivity
structural transformation
Tetrahydrofuran
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Summary:Using polyhedral oligomeric silsesquioxane (POSS) modified by a thiol group as a protected ligand, atom‐precise multi‐heteorocluster‐based dendrimers Ag12@POSS6 (1 a and 1 b) were assembled. Through the reactive −SH groups, six POSS shell ligands stabilize the central 12‐core silver(I) cluster by diverse Ag−S interactions. When such Ag12@POSS6 complex was stimulated by different solvents (acetone or tetrahydrofuran), the core Ag12 silver(I) cluster underwent reversible structural transformation between flattened cubo‐octahedral (in 1 a) and normal cubo‐octahedral (in 1 b); concomitantly shell POSS clusters rearranged from pseudo‐octahedral to quasi‐octahedral. Furthermore, the film matrix modified by 1 a or 1 b showed different hydrophobicity. An atom‐precise Ag12@POSS6 dendritic complex (POSS=polyhedral oligomeric silsesquioxane) has been synthesized. The central silver(I) cluster core underwent a reversible structural transformation with solvent stimuli, leading to the rearrangement of the shell POSS clusters from pseudo‐octahedral to quasi‐octahedral.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201807548