Controlled Self‐Assembly of Discrete Amphiphilic Oligourethanes with a Cascade Self‐Immolative Motif

Abstract

AbstractDiscrete polymers offer an excellent platform for comprehending the interplay between precise chain structures, distinctive self‐assembly behavior, and functional applications, whereas the development of discrete polymers with self‐immolative properties remains scarce. Here, we modularly synthesize a library of discrete self‐immolative oligourethanes containing N‐naphthylcarbamate or N‐(3‐fluorophenyl)carbamate repeating units via iterative stepwise growth. These oligourethanes undergo not only cascade 1,6‐elimination depolymerizations via photo‐mediated removal of o‐nitrobenzyl carbamate triggers but also selective cleavage of benzyl‐O linkages under MS/MS conditions even without UV light irradiation. In aqueous media, these discrete oligourethanes self‐assemble into different morphologies such as flat nanosheets, nanofibers, and nanoribbons, depending on the chain lengths and backbone compositions, and further morphological transitions are observed upon thermal annealing.