Aqueous Palladium‐Catalyzed Direct Arylation Polymerization of 2‐Bromothiophene Derivatives

Aqueous palladium‐catalyzed direct arylation polymerization (DArP) of 2‐bromothiophene derivatives 6‐(2‐(2‐bromothiophen‐3‐yl)ethoxy)hexyl trimethylammonium bromide (T1) and 4‐(2‐(2‐bromothien‐3‐yl)ethoxy)butylsulfonate (T2) is achieved. The supporting ligand, triphenylphosphine‐3,3′,3′′‐trisulfonic acid trisodium salt (m‐TPPTs), facilitates DArP of both derivatives; however, its separation from the polymers by dialysis is difficult due to its strong aggregation in water and N,N‐dimethylacetamide (DMAc). This is supported by dynamic light scattering, gel permeation chromatography (GPC), and single‐crystal X‐ray crystallography. Pyrimidine–Pd(OAc)2 is utilized in the DArP of T1 to afford PT1 without ligand contamination. Density functional theory calculations to determine the coordinating capability of the carboxylate/pivalic acid/water to palladium indicate the viability of implementing DArP in water. Finally, polyelectrolyte molecular‐weight overestimation by GPC in water is attributed to the polyelectrolyte effect. Aggregation of the conjugated polyelectrolytes leads to a contracted hydrodynamic volume, and the molecular weight and dispersity assessed by GPC in DMAc significantly deviate from the actual values. An objective approach to evaluate the molecular weight for conjugated polyelectrolytes requires further development. Direct arylation polymerization (DArP) of 2‐bromothiophene derivatives, T1 and T2, is achieved with the ligand m‐TPPTs, but with ligand contamination. Pyrimidine–Pd(OAc)2 is utilized in the DArP of T1 to afford PT1 without ligand contamination. The molecular weight and dispersity of the conjugated polyelectrolytes assessed by gel permeation chromatography in N,N‐dimethylacetamide significantly deviate from the actual values.