Advances in the controlled polymerization of conjugated polymers

Abstract

This article features recent advances in the synthesis of conjugated polymers via a controlled polymerization. These polymerizations typically rely on transition metal catalyzed cross coupling reactions. The mechanisms of the polymerization protocols are discussed in detail. An overview of all possible protocols and all homopolymers that have been investigated is given. Next, the synthesis of copolymers-random, gradient and block copolymers-is reviewed. Another advantage of a controlled polymerization is the possibility to introduce specific functional groups, either at the beginning of each polymer chain by the use of an external initiator, or at the end of the polymer chain using an endcapper. Finally, topologies different from simple linear polymer chains are discussed. This feature article is complementary to other recent review articles on this topic. 1,2

Influence of Branching of Polythiophenes on the Microporosity

“…The two CBr bonds constituted the active sites by which the catalyst can oxidatively insert and the propagation can both occur to give a hyperbranched structure . The CI bond, however, enabled a selective metalation of the precursor monomer prior to the in situ formation of the corresponding 5‐organozinc monomer (step (vi) in Scheme ) . The latter can therefore be polymerized via chain growth using a Pd(Ruphos) catalyst to give a well‐defined hyperbranched PT …”

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

“…It is critical to identify all the factors that enable chain‐growth polymerizations to promote wider use with a more diverse set of monomers . A number of excellent reviews have already appeared on this topic . In this Minireview, we will briefly highlight the choices for formation of active monomers (X and Y, Scheme ).…”

“…[47] An umber of excellent reviewsh ave already appeared on this topic. [24,25,44,[47][48][49][50][51][52] In this Minireview, we will briefly highlight the choices for formation of active monomers (X and Y, Scheme 1). Subsequently,w ew ill discuss the choice of metal and ancillary ligand with different conjugated systems;t his is perhaps the most important strategy to obtain control in CTP.F inally,w ew ill highlight future challenges and opportunities in the area.…”

Chain-Growth Horner-Wadsworth-Emmons Condensation Polymerization Initiated with an Aliphatic Aldehyde

“…Recently, lots of πconjugated polymers have been synthesized by transition-metal-catalyzed cross-coupling polycondensation methods [11,12]. Especially, a Catalyst-Transfer Polycondensation (CTP) system has been widely applied in this research area, because this system could precisely control the primary structures of polymers such as numberaverage molecular weight (M n ), Ð M , regioregularity and be accessible to block copolymers [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27]. However, it always requires both of halogenated monomers and transition-metal catalysts.…”