The tenth anniversary of Suzuki polycondensation (SPC)

Abstract

This article describes the successful transfer of the Suzuki cross-coupling (SCC) reaction to polymer synthesis, one of the major developments within the last decade of polymer synthesis. The polymers prepared by Suzuki polycondensation (SPC) and its Ni-catalyzed reductive counterpart are soluble and processable poly(arylene)s that, because of their rigid and conjugated backbones, are of interest for the materials sciences. Achievable molar masses easily compete with those of traditional polyesters and polyamides. This article also provides insight into some synthetic problems associated with the transfer of SCC from low molar mass organic chemistry to high molar mass polymer chemistry by addressing issues such as monomer purity, stoichiometric balance, achievable molar masses, and defects in the polymer structure. Although the emphasis of this article is synthetic and structural issues, some potential applications of the polyarylenes obtained are briefly mentioned. Together with the enormous developments in the areas of metallocene, ring-opening metathesis, and acyclic diene metathesis polymerization, the success of SPC impressingly underlines the increasing importance of transition-metal-catalyzed CC-bondforming reactions in polymer synthesis.

Development of catalyst‐transfer condensation polymerization. Synthesis of π‐conjugated polymers with controlled molecular weight and low polydispersity

“…[44][45][46] There have been several reports of model reactions for chain-growth Suzuki-Miyaura coupling polymerization, [47][48][49] but the chain-growth condensation polymerization had not been demonstrated yet. Furthermore, in chain-growth Suzuki-Miyaura coupling polymerization, stable arylpalladium(II) halide complex could be used as an externally added initiator, and the aryl group of the complex would serve as an initiator unit of the polymer.…”

The Controlled Polymerization of Poly(cyclopentadithiophene)s and Their All-Conjugated Block Copolymers

“…[1][2][3] Within the research area of CPs, there has been a clear synthetical evolution, starting from electrochemical and oxidative polymerizations, towards transition metal catalyzed polymerization mechanisms. [4][5][6][7] Herein, the transition metal catalyst forms a new C-C bond between two entities of which one carries a carbon-halogen bond, and the other one is, most frequently, an organometallic monomer system, although recent research also focuses on direct arylation where coupling takes place with a C-H bond instead of with an organometallic monomer. [8][9][10][11] The traditional transition metal catalyzed polymerization mechanisms generally proceed via a step-growth mechanism, and are still the most obvious choice for the synthesis of alternating copolymers.…”

Preparation of poly(fluorene)s using trans‐bis(dicyclohexylamine)palladium diacetate as a catalyst: Scope and limitations

“…Alternating copolymers are an important class of semiconducting materials, as they offer the possibility of designing their optoelectronic properties to maximize their application potential in areas such as organic photovoltaics, field-effect transistors, and light-emitting diodes. 11 For the broad scope of such polymers, endgroup modification provides another tool to fine-tune material properties by adding appropriate monofunctionalized comonomers. In this way, an attachment of defined functional groups, which are often chemically, chromophorically, or electronically active, can be achieved.…”