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. Polymerizations involve reacting a dialdehyde-functionalized dihydropyrrolopyrrole with p-phenylenediamine as the comonomer using p-toluenesulfonic acid as a catalyst. The inherent dynamic equilibrium of the azomethine bonds subsequently enabled the degradation of the polymers in solution in the presence of acid. Degradation of the polymers is monitored via NMR, UV-vis absorbance, and fluorescence spectroscopies, and the polymers are shown to be fully degradable. Notably, while absorbance measurements reveal a continued shift to higher energies with extended exposure to acid, fluorescence measurements show a substantial increase in the fluorescence response upon degradation. Results from this study encourage the continued development of environmentally-conscious polymerizations to attain polymeric materials with useful properties while simultaneously creating polymers with structural handles for end-of-life management or/and recyclability.

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. UV-vis spectroscopy and X-ray diffraction measurements show that the porphyrin-functionalized poly(3-hexylthiophene) exhibits increased intermolecular interactions with phenyl-C61-butyric acid methyl ester (PCBM) in the solid state compared to unfunctionalized poly(3-hexylthiophene) without sacrificing microstructure ordering that facilitates optimal charge transport properties. Additionally, differential scanning calorimetry revealed porphyrin-functionalized poly(3-hexylthiophene) crystallization decreased only slightly (1-6%) compared to unfunctionalized poly(3-hexylthiophenes) while increasing fullerene miscibility by 55%. Preliminary organic photovoltaic device results indicate device power conversion efficiency is sensitive to additive loading levels, as evident by a slight increase in power conversion efficiency at low additive loading levels but a continuous decrease with increased loading levels. While the increased fullerene miscibility is not balanced with significant increases in power conversion efficiency, this approach suggests that integrating non-bonded interaction potentials is a useful pathway for manipulating the morphology of the bulk heterojunction thin film, and porphyrin-functionalized poly(3-hexylthiophenes) may be useful additives in that regard.

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 0.35 for 1-TCM4PP, 0.75 for 5,10,15-tris(4-carbomethoxyphenyl)-20-(4-bromophenyl)porphyrin (2-TBCM3PP) and 0.88 for 5,10,15-tris(4-carbomethoxyphenyl)-20-(4-iodophenyl)porphyrin (3-TCM3IPP). Chemical quenching of 1,3-diphenylisobenzofuran and singlet oxygen emission studies rendered an average singlet oxygen quantum yield of 0.51, 0.75, and 0.90 for TCM4PP, TBCM3PP and TCM3IPP respectively. These photophysical properties indicate that a single halogen atom is capable of transforming TCM4PP into a sensitizer with strong triplet character. This is useful for generating singlet oxygen for photodynamic therapy, creating a long lasting reactive species for catalysis and for extending diffusion lengths in photovoltaic applications while retaining three molecular modification points for further functionalization.

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 1H NMR spectra indicate that the polymers will degrade in the presence of acid. After degradation, the aldehyde starting material was recovered in high yields and was shown to maintain structural integrity when compared with commercial starting materials. Solution-degradation studies found that rates of degradation vary from 5 h to 90 s depending on the choice of solvent or acid used for hydrolysis. Additionally, the polymer was shown to degrade in the presence of perfluoroalkyl substances (PFASs), which makes them potentially useful as PFAS-sensitive sensors. Ultimately, this research provides strategies to control the degradation kinetics of azomethine-containing polymers through the manipulation of environmental factors and guides the continued development of azomethine-based materials.

Expanding Color Control of Anodically Coloring Electrochromes Based on Electron-Rich 1,4-Dihydropyrrolo[3,2-b]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-b]pyrrole (DHPP) chromophores with varying functionalities along the 2,5-axis was envisioned to accomplish these goals. After predicting different absorbance traits as oxidized molecules with time-dependent density functional theory, DHPP chromophores with varying peripheral functionalities were synthesized in a single aerobic synthetic step via an iron-catalyzed multicomponent reaction and characterized as high-contrast chromophores. In solution, the DHPP chromophores absorb in the ultraviolet region of the electromagnetic spectrum, resulting in color-neutral L*a*b* color coordinates of ∼100, 0, 0. Upon chemical oxidation, each molecule transitions to absorb at various points across the visible spectrum based on the extent of electron-donating ability and can display five distinct colors. Importantly, the chromophores are redox-active and display switching capabilities with an applied electrochemical potential. In conjunction with building fundamental insights into molecular design of DHPP chromophores, the results and synthetic simplicity of DHPPs make them compelling materials for color-controlled high-contrast electrochromes.

Relating Design and Optoelectronic Properties of 1,4-Dihydropyrrolo[3,2-b]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-b]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. Solution oxidation studies found that variations in the electron-donating and -withdrawing capabilities result in different absorbance profiles of the radical cations that correspond to quantifiably different colors. In addition to fundamental insights into the molecular design of DHPP chromophores and their optoelectronic properties, two chromophores display high-contrast electrochromism, which makes them potentially compelling in electronic devices. Overall, this study represents the ability to fine-tune the optoelectronic properties of DHPP chromophores in their neutral and oxidized states and expands the understanding of structure-property relationships that will guide the continued development of DHPP-based materials.

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. In conjunction with these efforts, the utilization of Buchwald ligands in C-H/C-H cross coupling polymerizations also is reported, and variations in the ligand structure provide insight into the role ligand choice has on C-H cross-coupling polymerizations. Specifically, it is determined that the phosphine functionality affects the rate-determining, concerted metalation-deprotonation step of the catalytic cycle, while bulky isopropyl substituents on the ligand's lower aryl ring promote reductive elimination. By balancing these steric effects on the ancillary ligands, polymers are synthesized to exhibit molecular weights above the effective conjugation length, with recovered yields >90%. In addition to expanding the scope of conjugated polymers accessible via oxidative direct arylation polymerization, these results provide the foundational understanding for utilizing Buchwald-type ligands in C-H-activated polymerizations.

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. The multiester-functionalized polymer exhibits a relatively low onset of oxidation (∼0.4 V vs Ag/AgCl) and electrochromic character by transitioning from a colored neutral state to a colorless oxidized state with increasing potential in 0.1 M NaCl aqueous electrolyte. Additionally, the ester-functionalized polymer exhibits similar electrochromic properties in aqueous electrolytes when compared to traditional alkyl-substituted poly(3,4-propylenedioxythiophenes) in organic electrolytes, as evidenced by contrast values of ∼70% and switching speeds of ∼2 s. This work highlights the use of multipolar functionalities as a design strategy for synthesizing organic solvent processable, aqueous electrolyte compatible redox-active polymers without postpolymerization modifications or the sacrifice of electrochromic properties.

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. Specifically, thermal analyses show that poly(purine)s exhibit high thermal stability and high glass transition temperatures depending on the BDT side-chain substituents and substitution pattern of the purine-derived comonomer. Furthermore, optical properties measured via UV-vis and fluorescence spectroscopies show dependence on monomer substitution pattern. These findings demonstrate the viability of synthesizing poly(purine)s via metal-catalyzed cross-coupling reactions and highlight the potential to tailor poly(purine) properties via simple alterations of comonomers.