Cage-rearranged and cage-intact syntheses of azido-functionalized larger T10 and T12 POSSs.

Herein, we investigate the product type and distribution during the synthesis of azido-functionalized larger polyhedral oligomeric silsesquioxanes (POSSs) using 3-chloropropyl- and chloromethyldimethylsilylethyl-functionalized T8, T10, and T12 POSSs as precursors. Our findings indicate that cage rearrangement occurs for the 3-chloropropyl-functionalized POSS cages with a stability order of T12 > T10 > T8, while the chloromethyldimethylsilylethyl-functionalized POSS cages remain structurally intact after the nucleophilic substitution.

Engineering the Properties of Transparent Hybrid Coating toward High Hardness, Excellent Flexibility, and Multifunction.

Transparent functional coatings with glass-like hardness and polymer-like flexibility are highly desirable for flexible and foldable displays. Although several coatings have been developed toward this goal, achieving a functional coating with 9H pencil hardness and extremely low bending radius of curvature (rc) remains a great challenge due to the inherent conflict between hardness and flexibility. To overcome this trade-off, a facile strategy is developed herein. The coating is an organic-inorganic hybrid nanocomposite that is prepared from thiol-acrylate polymerization of acrylo polyhedral oligomeric silsesquioxane and multifunctional thiols. The former provides the desired hardness, while the latter affords high flexibility and the maximum level of chemical bonding for organic-inorganic phases. Because of the good miscibility and varied functionality of monomers, we are able to manipulate the composition and internal structure of coating systematically, endowing it with high transparency (98%, 550 nm), super hardness (9H), excellent low modulus (1.85 GPa, the most flexible one to date), and the ability to withstand steel wool's abrasion and repeated bending (rc = 0.8 mm) 10 000 times on PET film. On the final coating, both antifouling and antibacterial abilities are integrated without sacrificing its other properties after postfunctionalizing a zwitterionic layer. This work balances the hardness-flexibility conflict effectively and provides some useful protective coatings for next-generation displays.