Rational Use of Aromatic Solvents for Direct Arylation Polycondensation: C-H Reactivity versus Solvent Quality

The solvent for direct arylation polycondensation (DAP) is of crucial importance. For conjugated polymers exhibiting reduced solubility, the choice of solvent decides on the maximum molecular weight that can be achieved, hence, good aromatic solvents are generally desirable. However, unintentional activation of C-H bonds present in aromatic solvents under DAP conditions leads to in situ solvent termination which competes with step growth. Here we evaluate relative C-H reactivity and solvent quality of seven aromatic solvents for the DAP of defect-free naphthalene diimide (NDI)-based copolymers of different solubility. C-H reactivity is strongly reduced with increasing degree of substitution for both chlorine and methyl substituents. Mesitylene is largely C-H unreactive and, thus, albeit being a moderate solvent, enables very high molecular weights at elevated temperature for NDI copolymers with limited solubility.