Synthetic polymeric chemistry is one of the basic parts of polymer science

and highly efficient polymerization reactions are essential for the synthesis of high performance polymeric materials

for which the development of new synthetic methods for the emerging polymer science is of great importance.Bergman cyclization is a chemical process during which highly reactive aryl diradicals are formed from enediyne precursors.Bergman cyclization has shown strong impacts on a number of application fields including pharmaceutics

synthetic chemistry and material science.The diradicals intermediates stemmed from enediynes can cause DNA cleavage under physiological conditions

leading to the strong cytotoxicity of many naturally occurred enediyne antibiotics.Meanwhile

the diradicals intermediates can quickly couple with each other to construct polyarylenes

providing a novel method to synthesize this kind of conjugated polymers thanks to the advantages of facile operation

high efficiency

tailored structure and catalyst-free feature.Moreover

the conjugated polymers generated through Bergman cyclization show many remarkable properties

such as excellent thermal stability

good solubility and processability

which enables these polymers to be further manufactured into carbon-rich materials.In this article

a brief overview of the trajectory of Bergman cyclization in polymer science was introduced

followed by the introduction of the research advances mainly from our group in developing polymerization methods with Bergman cyclization

taking advantages of its catalyst-free

by-product-free features and in situ polymerization mechanism to synthesize new polymeric materials with various structures and morphology.These synthetic strategies include fabrication of rod-like polymers with polyester

dendrimer and chiral imide side chains

functionalization of carbon nanomaterials by surface-grafting conjugated polymers

formation of nanoparticles by intramolecular collapse of single polymer chains

construction of carbon nanomembranes on the external and internal surface of inorganic nanomaterials.These polymers with novel structural features were further used in a variety of fields like energy transformation

energy storage

catalyst support

and fluorescent detection.At the end of this article

an outlook of the future development of Bergman cyclization in medicinal chemistry and especially in polymer science is presented.