Construction of unsymmetrical open-cage silsesquioxanes

Abstract The introduction of chirality into siloxanes is crucial for applications in chiral separation, recognition, and reaction environments. Cage silsesquioxanes, with their distinct 3D structures, offer great potential in this field. Here, we utilized corner-opened polyhedral oligomeric silsesquioxane to construct unsymmetrical structures with cage-centered chirality. The three silanol groups of commercially available corner-opened polyhedral oligomeric silsesquioxanes were functionalized through a stepwise process. Efficient synthesis was achieved by selecting chlorosilanes with appropriate steric hindrance.