Synthesis of Highly Fluorescent All-Conjugated Alternating Donor–Acceptor (Block) Copolymers via GRIM Polymerization

Abstract

Although controlled polymerization procedures for conjugated polymers have considerable advantages with respect to molar mass and end group control, the material scope has been very limited, in particular considering block copolymers and donor-acceptor type all-conjugated polymers, imposing considerable challenges upon the synthetic polymer community. In this work, a push-pull monomer consisting of a thiophene (donor) and a pyridine (acceptor) unit is synthesized and subsequently polymerized via Kumada catalyst-transfer polymerization using a nickel catalyst (GRIM polymerization). In this way, an alternating donor-acceptor copolymer is obtained via a chain-growth mechanism. Furthermore, an all-conjugated block copolymer containing a poly(3-hexylthiophene) block and the alternating copolymer is successfully prepared in a one-pot procedure as well. The diblock structure is confirmed by comparison of the thermal, electrochemical and spectroscopic properties of the block copolymer and its constituting polymer parts.

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

“…Dppp and dppe nickel catalysts have also been used to tailor monomer composition in conjugated backbones, by polymerization of larger dimeric and trimeric monomers . Polymerizing oligomers is of particular interest because the metal must migrate over larger distances in the π‐system to produce chain‐growth.…”

“…Dppp and dppe nickel catalysts have also been used to tailor monomer compositioni nc onjugated backbones, by polymerization of larger dimeric and trimeric monomers. [95,103,112,[128][129][130][131] Polymerizing oligomers is of particulari nterest because the metal must migrate over larger distances in the p-system to produce chain-growth. The fact that these reactions proceed in ac ontrolled manner highlightst he potential for larger p-electronf rameworks in CTP.B ielawski and coworkers recently reported that Ni(dppp)Cl 2 can polymerize a donor-acceptor thiophene-benzotriazolea lternating polymer, which is an exciting development for further investigation.…”

Investigation of Bimetallic Nickel Catalysts in Catalyst‐Transfer Polymerization of π‐Conjugated Polymers

“…The discovery of this controlled polymerization has advanced the field of π‐conjugated polymer synthesis; however, the scope of CTP has been limited to simple and electron‐rich monomers . Progress has been made to use electron‐deficient monomers, but successful CTP methodologies remain scarce . Success or failure of CTP is strongly dependent on the stability of the metal–polymer π‐complex.…”

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monomers, but successful CTP methodologies remain scarce. [9][10][11][12] Success or failure of CTP is strongly dependent on the stability of the metal-polymer π-complex. A weaker metal-polymer π-complex has been observed with electron-deficient monomers in CTP.

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Yellow electrochromic polymer materials with fine tuning electrofluorescences by adjusting steric hindrance of side chains

“…Thiophene derivatives with long side chains have been widely used in soluble electrochromic polymer materials, as they exhibited unique advantages such as tunable colors, facial processing procedure, high coloration efficiency and short response time. [12][13][14][15][16] However, these thiophene derivatives polymers have strongly aggregation-caused quenching (ACQ) effect, 17 which limits the uorescent application in a state of aggregation, such as particles or lm. In order to design the above mentioned bifunctional material, oxadiazole derivatives, excellent uorescent functional molecule, 18,19 was introduced in polymer backbone to act as electrouorescent functional group.…”