Understanding Degradation Dynamics of Azomethine-containing Conjugated Polymers.

Understanding the influence of chemical environments on the degradation properties of conjugated polymers is an important task for the continued development of sustainable materials with potential utility in biomedical and optoelectronic applications. Azomethine-containing polymers were synthesized via palladium-catalyzed direct arylation polymerization (DArP) and used to study fundamental degradation trends upon exposure to acid. Shifts in the UV-vis absorbance spectra and the appearance/disappearance of aldehyde and imine diagnostic peaks within the H NMR spectra indicate that the polymers will degrade in the presence of acid.

Expanding Color Control of Anodically Coloring Electrochromes Based on Electron-Rich 1,4-Dihydropyrrolo[3,2-]pyrroles.

Anodically coloring electrochromes have received attention in recent years as high-contrast alternatives to cathodically coloring electrochromes due to their superior optical contrast during electrochemical switching. While current systems represent significant progress for organic electrochromics, it is necessary to expand the structural diversity of these materials while simultaneously reducing the hazards associated with synthetic protocols. With these considerations in mind, a family of 1,4-dihydropyrrolo[3,2-]pyrrole (DHPP) chromophores with varying functionalities along the 2,5-axis was envisioned to accomplish these goals.

Relating Design and Optoelectronic Properties of 1,4-Dihydropyrrolo[3,2-]pyrroles Bearing Biphenyl Substituents.

Understanding the influence of peripheral functionality on optoelectronic properties of conjugated materials is an important task for the continued development of chromophores for myriad applications. Here, π-extended 1,4-dihydropyrrolo[3,2-]pyrrole (DHPP) chromophores with varying electron-donating or electron-withdrawing capabilities were synthesized via Suzuki cross-coupling reactions, and the influence of functionality on optoelectronic properties was elucidated. First, chromophores display distinct differences in the UV-vis absorbance spectra measured via UV-vis absorbance spectroscopy in addition to changes in the onset of oxidation measured with cyclic voltammetry and differential pulse voltammetry.

Azomethine-Containing Pyrrolo[3,2-b]pyrrole Copolymers for Simple and Degradable Conjugated Polymers.

Conjugated polymers have received significant attention as potentially lightweight and highly tailorable alternatives to inorganic semiconductors, but their synthesis is often complex, produces toxic byproducts, and they are not typically designed to be degradable or recyclable. These drawbacks necessitate dedicated efforts to discover materials with design motifs that enable targeted and efficient degradation of conjugated polymers. In this vein, the synthetic simplicity of 1,4-dihydropyrrolo[3,2-b]pyrroles (DHPPs) is exploited to access azomethine-containing copolymers via a benign acid-catalyzed polycondensation protocol.

Tuning fullerene miscibility with porphyrin-terminated P3HTs in bulk heterojunction blends.

Understanding and manipulating the miscibility of donor and acceptor components in the active layer morphology is important to optimize the longevity of organic photovoltaic devices and control power conversion efficiency. In pursuit of this goal, a "porphyrin-capped" poly(3-hexylthiophene) was synthesized to take advantage of strong porphyrin:fullerene intermolecular interactions that modify fullerene miscibility in the active layer. End-functionalized poly(3-hexylthiophene) was synthesized via catalyst transfer polymerization and subsequently functionalized with a porphyrin moiety via post-polymerization modification.

Exploring the Utility of Buchwald Ligands for C-H Oxidative Direct Arylation Polymerizations.

Oxidative C-H/C-H cross-coupling polymerizations provide an opportunity to synthesize conjugated polymers with an increased ease of monomer preparation, reduced environmental impact, and increased sustainability. Considering these attributes, it is necessary to expand the diversity of monomers that readily and efficiently participate in this coupling strategy to enable the development of conjugated polymers with a wide range of properties. Herein, the oxidative direct arylation polymerization toolbox is expanded to include 3,4-propylenedioxythiophene being synthesized via C-H/C-H cross-coupling methodologies.

Aqueous Electrolyte Compatible Electrochromic Polymers Processed from an Environmentally Sustainable Solvent.

Developing aqueous electrolyte compatible, redox-active polymers that can be processed from environmentally sustainable solvents is desirable because these traits will effectively reduce environmental impact and human health hazards during processing procedures and in the final device architecture. To achieve organic solvent solubility and aqueous compatibility, a poly(3,4-propylenedioxythiophene) containing four ester functionalities was synthesized via direct arylation polymerization. The resulting polymer was spray-cast into a thin film from the environmentally sustainable solvent 2-methyltetrahydrofuran, and the presence of multiple polar functionalities rendered the film aqueous electrolyte compatible.

Synthesis of Main Chain Purine-Based Copolymers and Effects of Monomer Design on Thermal and Optical Properties.

The ability to incorporate diverse monomeric building blocks enables the development of advanced polymeric materials possessing a wide range of properties that suits them for myriad applications. Herein, that synthetic toolbox is expanded through the first report of purine-based copolymers in which purines are incorporated directly into the polymer main chain. Stille cross-coupling of dibromopurine monomers with benzodithiophene (BDT) comonomers is used to generate these "poly(purine)s", and variations in the substitution pattern of the purine monomer and BDT side-chains provides insight into the role of monomer design on their resultant thermal and photophysical properties.

Efficient intersystem crossing using singly halogenated carbomethoxyphenyl porphyrins measured using delayed fluorescence, chemical quenching, and singlet oxygen emission.

Sensitizers with high triplet quantum yields are useful for generating photovoltaics, photocatalysts and photodynamic therapy agents with increased efficiency. In this study, the heavy atom effect was used to optimize the triplet and singlet oxygen quantum yields of 5,10,15,20-tetrakis(4-carbomethoxyphenyl)porphyrin (1-TCM4PP). The triplet quantum yields, determined using delayed fluorescence, was calculated as 0.