Polyhedral Oligomeric Silsesquioxane Hybrid Polymers: Well‐Defined Architectural Design and Potential Functional Applications

Polyhedral oligomeric silsesquioxane (POSS)‐hybrid polymers have been successfully employed as functional inorganic–organic hybrid materials for various applications due to their well‐determined structures. The past 6 years has witnessed growing interest in the rational design and synthetic approaches for POSS‐hybrid polymers, driven by the adoption of controlled living radial polymerization and click chemistry. This review addresses developments in the precise manipulation of POSS building blocks via atom transfer radical polymerization, reversible addition–fragmentation chain transfer, and click chemistry. Not only are the structures of POSS‐hybrid polymers tunable in terms of chemical composition, molecular weight, and polydispersity, but they are also controllable in sequential and hierarchical chain topology. Finally, some representative cutting‐edge applications of POSS‐hybrid polymers, including biomedical and energy‐related materials, fabrication of nanostructures, and functional surface coating materials, are highlighted. Polyhedral oligomeric silsesquioxane (POSS)‐containing building blocks are crucial for achieving desirable structures of POSS‐hybrid polymers by properly adopting different polymerization techniques. Owing to the diversity of its hierarchical structure, POSS‐hybrid polymers present satisfying controllability in terms of self‐assembly behavior and aggregation state, which has empowered polymer chemists with the ability to prepare various POSS‐hybrid polymers for potential applications.