The architectural evolution of self-immolative polymers

Self-immolative polymers (SIPs) depolymerize to small molecules through a cascade of reactions following cleavage of the polymer backbone or a specific terminal or focal point moiety by a stimulus. They have been developed using the principles of self-immolative spacers and low ceiling temperature (Tc) polymers. Key developments over the past couple of decades have been the polymerization of spacers to enable long reaction cascades, and the introduction of stimuli-responsive end-caps which have allowed depolymerization to be triggered in a controlled manner in response to a wide array of stimuli. This review will focus on the architectural evolution of SIPs over the past two decades from oligomers to dendrimers, linear polymers, cyclic polymers, graft copolymers, networks, and hyperbranched systems. We will discuss how the architecture influences the triggering and propagation of the reaction cascade and highlight how different architectures can provide advantages and disadvantages in terms of their synthesis and properties. [Display omitted] •Self-immolative polymers translate a single bond cleavage event into a depolymerization cascade.•Early examples were oligomers and dendrimers, then linear and cyclic polymers were developed.•Recent examples have evolved to include graft copolymers and cross-linked networks.