Polymer Architectures Built From Anthryl‐Containing Polystyrene and Their Topological Conversions

ABSTRACT This study elaborates on the preparation of anthryl‐containing polymers and their effective topological conversions conducted by dimerization of anthryl and cleavage of the anthryl dimer. A multifunctional polystyrene (PS) macroinitiator capped with anthryl groups at both chain ends is prepared and used in atom transfer radical polymerization (ATRP) of styrene to afford a triblock PS. Twin‐tail tadpole‐shaped and centipede‐shaped polymers are obtained by photoirradiation of triblock PS at 365 nm due to the dimerization of anthryl. The tadpole‐shaped and centipede‐shaped polymers are able to convert back to linear topology via the cleavage of anthryl dimer by photoirradiation at 280 nm or heating at 150°C. A multicyclic polymer with a repeating linear‐ring structure is afforded by atom transfer radical coupling (ATRC) reaction of twin‐tail tadpole‐shaped PS, and its conversion to a multi‐block linear topology is also realized.