Synthesis of conjugated copolymers by combining different coupling reactions

Abstract

Different coupling reactions are combined in the same copolymerization to tune the structure of the resulting conjugated copolymer.

Air‐tolerant poly(3‐hexylthiophene) synthesis via catalyst‐transfer polymerization

“…Combined, these results suggest that the slower polymerization is not due to monomer quenching with adventitious moisture but instead that the Zn(OPiv) 2 ‐based monomer is more nucleophilic, leading to a faster polymerization. The different reactivities of the Zn and Mg monomers may be useful for generating random, gradient, and block copolymers in situ 35 . Our earlier results (Table 1) also indicate that the form of ZnX 2 (where X = OPiv or Cl) plays an important, yet still not well‐defined role, because the polymerization was slower with ZnCl 2 .…”

Diversifying Cross‐Coupling Strategies, Catalysts and Monomers for the Controlled Synthesis of Conjugated Polymers

“…[37,38,59,[63][64][65][66][67][68] Stille-Migita coupling (X-Ar-SnR 3 )i sp erhaps the mildest coupling methodu sed to date, thougha lso the least reactive for CTP ( Figure 1). [39,69,70] The tin species used in the formation of these monomers and the tin byproducts of the coupling are toxic, which is al imitation of this polymerization strategy.A urylated monomers (X-Ar-AuPtBu 3 )a re a recent addition to the family of controlled polymerizations. [69,71]…”

“…[39,69,70] The tin species used in the formation of these monomers and the tin byproducts of the coupling are toxic, which is al imitation of this polymerization strategy.A urylated monomers (X-Ar-AuPtBu 3 )a re a recent addition to the family of controlled polymerizations. [69,71]…”

“…Both sequential addition and end group functionalization can be used as synthetic strategies to prepare these types of materials. Architectures such as gradient [69,97,114,132] and star [133] copolymersh ave also been targeted and synthesized.…”

“…Organoboron reagents (Suzuki–Miyaura coupling) have become a reagent of choice due to the functional group tolerance of this reaction, and the environmentally benign, boronic acid byproducts . Stille–Migita coupling (X‐Ar‐SnR 3 ) is perhaps the mildest coupling method used to date, though also the least reactive for CTP (Figure ) . The tin species used in the formation of these monomers and the tin byproducts of the coupling are toxic, which is a limitation of this polymerization strategy.…”