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

Si Li; Zhao-Yang Wang; Guang-Gang Gao; Bing Li; Peng Luo; Yu-Jin Kong; Hong Liu; Shuang-Quan Zang

doi:10.1002/anie.201807548

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

Angew Chem Int Ed Engl. 2018 Sep 24;57(39):12775-12779. doi: 10.1002/anie.201807548. Epub 2018 Aug 30.

Authors

Si Li¹, Zhao-Yang Wang¹, Guang-Gang Gao², Bing Li¹, Peng Luo¹, Yu-Jin Kong¹, Hong Liu², Shuang-Quan Zang¹

Affiliations

¹ College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, 450001, China.
² School of Materials Science and Engineering, University of Jinan, Jinan, 250022, China.

PMID: 30106215
DOI: 10.1002/anie.201807548

Abstract

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.

Keywords: clusters; polyhedral oligomeric silsesquioxanes; silver; solvent sensitivity; structural transformation.

Abstract

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