Functionalizable, Side Chain-Immolative Poly(benzyl ether)s

Herein, we report a poly­(benzyl ether)-based self-immolative polymer (SIP) with pendant pyridine disulfide groups. Cleavage of the side-chain disulfides leads to the formation of phenolates, which initiate depolymerization from the side chain. Due to the higher density of the disulfide groups compared to that of the chain-end-capping group, which normally is responsible for initiating depolymerization of SIPs, the side chain-immolative polymer (ScIP) can be readily degraded in the solid state where the mobility of polymer chains is substantially limited. The ScIP was also further modified through the thiol–disulfide exchange reaction to prepare ScIP-g-poly­(ethylene glycol) graft polymers and organogels, which were also able to undergo complete reductive self-immolative degradation.