Macromolecular Rapid Communications, Journal Year: 2025, Volume and Issue: unknown
Published: April 24, 2025
Abstract High‐molar‐mass π ‐conjugated polymers (CPs) are essential for semiconductor applications. However, conventional step‐growth cross‐coupling polymerizations generally require strict monomer stoichiometry according to the Carothers/Flory theory. Herein, an environmentally benign nonstoichiometric direct arylation polymerization (DArP) is reported that efficiently affords high‐molar‐mass CPs without employing metal‐containing monomers or silver salts. Specifically, 3,4‐ethylenedioxythiophene polymerized using up a 3‐fold excess of 4,9‐dibromo‐2,7‐bis(2‐decyltetradecyl)benzo[ lmn ][3,8]‐phenanthroline‐1,3,6,8‐tetraone in presence catalytic Pd 2 (dba) 3 /(4‐dimethylaminophenyl)di‐ tert ‐butylphosphine (AmPhos), affording with number‐average molar masses far exceeding theoretical values predicted equation. Model reactions involving 2,3‐dihydrothieno[3,4‐ b ][1,4]dioxine‐5‐carbonitrile and 4,9‐dibromo‐2,7‐bis(2‐hexyl)benzo[ indicate electron‐rich AmPhos ligand promotes intramolecular catalyst transfer (“ring‐walking”), enabling high efficiency even under conditions. The resulting exhibit negligible structural defects good solubility common organic solvents, suggesting regioselective minimal side reactions. proposed DArP approach may offer advantages such as reduced times by readily accessible high‐performance semiconducting polymers.
Language: Английский