Conjugated polymers find applicability in numerous technologies, but wide-spread commercialization remains elusive, mostly due to synthetic accessibility. Specifically, most polymer systems require multiple synthetic steps, with each step generating waste that influences cost and environmental considerations, or air/moisture-free and cryogenic reaction conditions. As a means to eliminate these hurdles, pyrrolo[3,2-b]pyrroles (H2DPPs) provide a new approach for synthesizing monomers that will participate in metal-catalyzed cross-coupling polymerizations and access a diverse class of semiconducting polymers. H2DPPs are excellent candidates for this because monomers are accessible in one or two synthetic steps (depending on the desired functionality) from commercially relevant starting materials (anilines and aldehydes) and monomer synthesis is performed in air. The first thrust of this project is to synthesize dihalogenated H2DPPs and establish design principles to create monomers with adequate solubility in reaction media and reactivity in Pd-catalyzed cross-coupling reactions (Suzuki, Stille, Direct Arylation, for example). Results from this thrust will guide polymerization conditions (catalyst, solvent, temperature, etc.) used in the second thrust, where the first example of poly(H2DPPs) will be achieved. Fundamental design-structure-property-relationships are established by studying synthesized polymers with optical (absorbance and fluorescence spectroscopies), electrochemical (cyclic voltammetry and differential pulse voltammetry), and thermal (thermal gravimetric analysis and differential scanning calorimetry) characterization techniques. Outcomes from this work provide foundational information regarding a new monomeric building block and will guide the continued development of a highly-tailorable, synthetically-addressable scaffold to create polymeric materials with targeted properties.

Simplified synthesis of conjugated polymers facilitated via pyrrolo[3,2-b]pyrroles

ACS Fall 2021

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