Issue 3, 2014

Tuning “thiol-ene” reactions toward controlled symmetry breaking in polyhedral oligomeric silsesquioxanes

Abstract

The convenient synthesis of nano-building blocks with strategically placed functional groups constitutes a fundamental challenge in nano-science. Here, we describe the facile preparation of a library of mono- and di-functional (containing three isomers) polyhedral oligomeric silsesquioxane (POSS) building blocks with different symmetries (C3v, C2v, and D3d) using thiol-ene chemistry. The method is straightforward and general, possessing many advantages including minimum set-up, simple work-up, and a short reaction time (about 0.5 h). It facilitates the precise introduction of a large variety of functional groups to desired sites of the POSS cage. The yields of the monoadducts increase significantly using stoichiometric amounts of bulky ligands. Regio-selective di-functionalization of the POSS cage was also attempted using bulky thiol ligands, such as a thiol-functionalized POSS. Electrospray ionization (ESI) mass spectrometry coupled with travelling wave ion mobility (TWIM) separation revealed that the majority of diadducts are para-compounds (∼59%), although meta-compounds (∼20%) and ortho-compounds (∼21%) are also present. Therefore, the thiol-ene reaction provides a robust approach for the convenient synthesis of mono-functional POSS derivatives and, potentially, of regio-selective multi-functionalized POSS derivatives as versatile nano-building blocks.

Graphical abstract: Tuning “thiol-ene” reactions toward controlled symmetry breaking in polyhedral oligomeric silsesquioxanes

Supplementary files

Article information

Article type
Edge Article
Submitted
29 Sep 2013
Accepted
18 Nov 2013
First published
18 Nov 2013

Chem. Sci., 2014,5, 1046-1053

Author version available

Tuning “thiol-ene” reactions toward controlled symmetry breaking in polyhedral oligomeric silsesquioxanes

Y. Li, K. Guo, H. Su, X. Li, X. Feng, Z. Wang, W. Zhang, S. Zhu, C. Wesdemiotis, S. Z. D. Cheng and W. Zhang, Chem. Sci., 2014, 5, 1046 DOI: 10.1039/C3SC52718B

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