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

Abstract

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

“…Based on the abovementioned unique advantages, synthetic POSS compounds manifested the extended application in various fields ranging from biomedicine, magnetic nanodevices, microsensors, molecular bioreactors and microelectronic devices. [ 89 ] Owing to the presence of Si—O and Si—C bonds constituting the POSS skeleton, the biological inert feature and low inflammatory response made them attractive exploration objects in the field of tailor‐made biomedical applications. As favored option in biomaterials, POSS‐based hybrid materials were first introduced into breast surgery in the 1960s, which are non‐toxic and cytocompatible compared with conventional carbon‐based nanotubes.…”

“…Except for the star‐like POSS‐based hybrid materials described previously, the copolymers involved in two or more polymerized monomers could be fabricated by halogen‐terminal homopolymer, which contained POSS moieties as ATRP initiator. [ 89 ] According to the sequential polymerization, the star‐like POSS‐ g ‐(PDMA‐ b ‐ Psulfo) 8 with multiple arm structure could be precisely synthesized by subtle structural design. Starting from the functionalization of POSS‐(NH 3 Cl) 8 modified by BiBB, the resultant product subsequently mixed with DMA as monomers, following the addition of sulfo moieties in desired order.…”

Formation of Bifunctional Octasilsesquioxanes via Silylative Coupling and Cross-Metathesis Reaction

“…Polyhedral oligosilsesquioxanes with the general formula (RSiO 3/2 ) n are currently one of the most attractive organosilicon compounds [ 1 , 2 ]. Among many advantages of these compounds, i.e., exclusive properties derived from a chemically and thermally robust organic-inorganic framework, and tailor-made three-dimensional structures, the ease of their modification by many synthetic methods is of the utmost importance.…”

“…They are all dependent on the type of the functional group attached to the Si–O–Si (SiHC=CH 2 , SiH SiOH). The utilization of these multiple protocols provides a wide range of inorganic/organic hybrid systems that find great application potential in material chemistry, optics, electronics, and catalysis, as well as in medical science [ 2 , 24 , 25 , 26 ].…”

Polysiloxanes Grafted with Mono(alkenyl)Silsesquioxanes—Particular Concept for Their Connection

“…Silsesquioxanes represent a versatile group of organosilicon species, with distinct and defined structures, but the most popular are cage silsesquioxanes, especially cubic T 8 [56,57]. Rigid inorganic, Si-O-Si based core with organic substituents (reactive or inert) coordinated around the silicon vertices, determine properties and potential application of these molecules [58][59][60][61][62][63][64]. The most significant branch of SQs successful application is material chemistry as nanofillers and polymers modifiers [65][66][67][68][69][70][71].…”