Block and Random Living, Ring-Opening Metathesis Copolymerization of Functionally Differentiated Carbazole-Containing Norbornene Monomers

The synthesis of novel diblock polymers containing both a potential charge transport and a non‐linear optic block has been accomplished. The synthesis exploits the living, ring‐opening metathesis block copolymerization of two norbornene type monomers, one of which contains an unsubstituted N‐carbazolyl ring while the other has a bromo substituent at the 3‐position of the carbazole ring. Conversion of the bromo functionality to a 2,2‐dicyanovinyl group introduces the non‐linear optic property. The first monomer was prepared by the previously reported efficient cation radical Diels–Alder cycloaddition of N‐trans‐1‐propenylcarbazole to 1,3‐cyclopentadiene, while the second was obtained by N‐bromosuccinimide bromination of the first monomer. For purposes of comparison, the corresponding random copolymer was also synthesized.