Synthesis of Poly(bisisoindigo) Using a Metal-free Aldol Polymerization for Thin-Film Transistor Applications.

Typical syntheses of conjugated polymers rely heavily on organometallic reagents and metal-catalyzed cross-coupling reactions. Here we show that an environmentally-benign aldol polymerization can be used to synthesize poly(bisisoindigo), an analog of polyisoindigo with a ring-fused structural repeat unit. Owing to its extended conjugation length, poly(bisisoindigo) absorbs across the UV/vis/NIR spectrum, with an absorption tail that reaches 1000 nm. Due to the four electron-deficient lactam units on each repeat unit, poly(bisoindigo) possesses a low-lying LUMO, which lies at -3.94 eV relative to vacuum. Incorporation of the ring-fused monomer unit also lowered the overall torsional strain in the polymer backbone (relative to polyisoindigo), and the polymer was successfully used in prototype unipolar n-channel organic thin-film transistors.