Polyhedral Oligomeric Silsesquioxanes (POSS)‐based Hybrid Materials: Molecular Design, Solution Self‐Assembly and Biomedical Applications

Abstract Owing to the tremendous advantages and unique well‐defined nanoscale structure, polyhedral oligomeric silsesquioxanes (POSS) have received considerable interest in the design of novel organic‐inorganic hybrid nanomaterials with all manner of prominent capabilities, which is recognized as a new generation of promising materials for advanced applications of material science, engineering science and biomedical fields. Benefitting from the recent progress in combination of controlled/living polymerization and emerging click chemistry, POSS‐based hybrid materials with ingenious design, versatile topological structure and sophisticated multifunctionality have been successfully fabricated and developed into abundant well‐defined hybrid nanostructures with desired physicochemical properties. Tailor‐made amphiphilic molecular design and nanosized hybrid architecture provide opportunities for the self‐assembly of POSS‐based hybrid materials with unique hierarchical morphologies in selective solvents. Through the in‐depth understanding of structure‐properties relationship, POSS‐based hybrid materials can achieve the modulation of precise control of self‐assembling process and multi‐purpose applications with improved material performances. In this review, we summarize the recent advances of POSS‐based hybrid materials in molecular design, self‐assembly behavior in solutions and potential biomedical applications with main concerns on drug delivery, gene therapy, bioimaging and tissue engineering field. Finally, future directions and remaining challenges for further advancement of POSS‐based hybrid materials are proposed and discussed.