Pyrazinacene conjugated polymers: a breakthrough in synthesis and unraveling the conjugation continuum.

Pyrazinacenes are next generation N-heteroacenes and represent a novel class of stable n-type materials capable of accepting more than one electron and displaying intriguing features, including prototropism, halochromism, and redox chromism. Astonishingly, despite a century since their discovery, there have been no reports on the conjugated polymers of pyrazinacenes due to unknown substrate scope and lack of pyrazinacene monomers that are conducive to condensation polymerization. Breaking through these challenges, in this work, we report the synthesis of previously undiscovered and highly coveted conjugated polymers of pyrazinacenes. In order to understand the intricacies of conjugation extension within the acene and along the polymer backbone, a series of electronically diverse four pyrazinacene conjugated polymers were synthesized. Polymers synthesis required optimizing a few synthetic steps along the 12-step synthetic pathway. The generated pyrazinacene monomers are not amenable to the popular condensation polymerizations involving Pd or Cu catalysts. Gratifyingly, Pd and Cu free dehydrohalogenation polymerization of the monomer with HgCl2 resulted in high molecular weight organometallic conjugated pyrazinacene polymers within a few minutes at room temperature. The dual role played by the Hg(ii) during the polymerization, combined with the self-coupling of the RHgCl (intermediate), is at the core of successful polymerization. Notably, the self-coupling of intermediates challenges the strict stoichiometric balance typically required for step-growth polymerization and offers a novel synthetic strategy to generate high molecular weight conjugated polymers even with imbalanced monomer stoichiometries. A combination of electrochemical studies and DFT-B3LYP simulations indicated that the presence of the reduced pyrazine ring promotes interacene π-conjugation through the metal center, in contrast to completely oxidized tetrazaazaanthracene. The extension of conjugation results in ca. 2 eV lower reduction potential for polymers compared to the monomer, placing the LUMO energy levels of these polymers on par with some of the best-known n-type polymers. Also, the presence of NH protons in the pyrazinacene polymers show ionochromism and red-shift UV-vis absorption maximum by ca. 100 nm. This work not only shows a way to realize highly desirable and elusive pyrazinacene conjugated polymers but also paves the way for a library of n-type conjugated polymers that can undergo multi-electron reduction.

Using molecular straps to engineer conjugated porous polymer growth, chemical doping, and conductivity.

Controlling network growth and architecture of 3D-conjugated porous polymers (CPPs) is challenging and therefore has limited the ability to systematically tune the network architecture and study its impact on doping efficiency and conductivity. We have proposed that π-face masking straps mask the π-face of the polymer backbone and therefore help to control π-π interchain interactions in higher dimensional π-conjugated materials unlike the conventional linear alkyl pendant solubilizing chains that are incapable of masking the π-face. Herein, we used cycloaraliphane-based π-face masking strapped monomers and show that the strapped repeat units, unlike the conventional monomers, help to overcome the strong interchain π-π interactions, extend network residence time, tune network growth, and increase chemical doping and conductivity in 3D-conjugated porous polymers. The straps doubled the network crosslinking density, which resulted in 18 times higher chemical doping efficiency compared to the control non-strapped-CPP. The straps also provided synthetic tunability and generated CPPs of varying network size, crosslinking density, dispersibility limit, and chemical doping efficiency by changing the knot to strut ratio. For the first time, we have shown that the processability issue of CPPs can be overcome by blending them with insulating commodity polymers. The blending of CPPs with poly(methylmethacrylate) (PMMA) has enabled them to be processed into thin films for conductivity measurements. The conductivity of strapped-CPPs is three orders of magnitude higher than that of the poly(phenyleneethynylene) porous network.

Controlling π-Conjugated Polymer-Acceptor Interactions by Designing Polymers with a Mixture of π-Face Strapped and Nonstrapped Monomers.

Controlling π-conjugated polymer-acceptor complex interaction, including the interaction strength and location along the polymer backbone, is central to organic electronics and energy applications. Straps in the strapped π-conjugated polymers mask the π-face of the polymer backbone and hence are useful to control the interactions of the π-face of the polymer backbone with other polymer chains and small molecules compared to the conventional pendant solubilizing chains. Herein, we have synthesized a series of strapped π-conjugated copolymers containing a mixture of strapped and nonstrapped comonomers to control the polymer-acceptor interactions. Simulations confirmed that the acceptor is directed toward the nonstrapped repeat unit. More importantly, strapped copolymers overcome a major drawback of homopolymers and display higher photoinduced photoluminescence (PL) quenching, which is a measure of electron transfer from the polymer to acceptor, compared to that of both the strapped homopolymer and the conventional polymer with pendant solubilizing chains. We have also shown that this strategy applies not only to strapped polymers, but also to the conventional polymers with pendant solubilizing chains. The increase in PL quenching is attributed to the absence of a steric sheath around the comonomers and their random location along the polymer backbone, which enhances the probability of non-neighbor acceptor binding events along the polymer backbone. Thus, by mixing insulated and noninsulated monomers along the polymer backbone, the location of the acceptor along the polymer backbone, polymer-acceptor interaction strength, and the efficiency of photoinduced charge transfer are controllable compared to the homopolymers.

Molecular tetrominoes: selective masking of the donor π-face to control the configuration of donor-acceptor complexes.

Understanding the doping mechanism in organic semiconductors and generating molecular design rules to control the doping process are crucial for improving the performance of organic electronics. Even though controlling the location and orientation of the dopant along the semiconductor backbone is an important step in the doping mechanism, studies in this direction are scarce as it is a challenging task. To address this, herein, we incorporated π-face masked (strapped) units in 1,4-bis(phenylethynylene)benzene (donor) to control the acceptor (dopant) location along the trimer, donor-acceptor binding strength, and acceptor ionization. Two strapped trimers, PCP and CPC, are synthesized with control over the location of the strapped repeat unit in the trimer. The trimers are complexed with the 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) acceptor in solution. DFT calculations show that DDQ residing on the non-strapped repeat unit (the percentage of this configuration is at least ca. 73%) has the highest binding energy for both PCP and CPC. The percentage of dopant ionization is higher in the case of strapped trimers (PCP and CPC) compared to that of linear control trimers (PLP and LPL) and the completely non-strapped (PPP) trimer. The percentage of dopant ionization increased by 15 and 59% in the case of PCP and CPC respectively compared to that of PPP.

Role of Aryl Amphiphile Hydrophobe Size on the Concentration and Stability of Graphene Nanoplatelet Dispersions.

Graphene nanoplatelets (GNPs) are stable and relatively inexpensive compared to single-layer graphene sheets and carbon nanotubes and are useful in diverse electronic, optoelectronic, and mechanical applications. Solution-state processing of the active material is desired in most of the applications mentioned above, and thus, there is great interest in increasing the concentration and stability of GNP suspension. Herein, to elucidate the role of the stabilizer structural parameters on the concentration and stability of GNP dispersions, we synthesized and used a series of aryl amphiphiles (ArAs) of varying aryl hydrophobe sizes and geometries. The ArAs were found to generate GNP dispersions with concentrations ranging from 0.05 to 0.13 mg mL-1 depending on the size of the aryl hydrophobe. The ArAs' hydrophobe size played a key role in determining the concentration of GNP suspension, while ArAs' critical aggregation concentration and solubility limits had no impact on the GNP suspension concentration. Most of the studied ArAs work similar to methylcellulose, the previously reported best performing stabilizer . Moreover, the ArAs stabilized the GNP suspension better than methylcellulose and were able to form stable dispersions for up to 6 h. Raman studies indicate that the quality of the GNPs did not degrade during the dispersion process. These findings will aid in the development of design rules for next-generation stabilizers.

Waveguiding properties of perylene microcrystals synthesized by retarding the growth along the π-stack direction.

Selective, hard to realize growth retardation of the π-stacking direction over the edge-packing direction has been achieved in perylene microcrystals using an aryl amphiphile. The perylene microcrystals grow predominantly along the edge-packing direction resulting in novel and hitherto unknown perylene square rods. The rods show exciton-polariton waveguiding along the rod axis even though it corresponds to pure edge-packing of the molecules, which is unprecedented in organic microcrystals.

ß-Strand inspired bifacial π-conjugated polymers.

Access to diverse, relatively high molecular weight soluble linear polymers without pendant solubilizing chains is the key to solution state synthesis of structurally diverse nanoribbons of conjugated materials. However, realizing soluble 1D-π-conjugated polymers without pendant solubilizing chains is a daunting task. Herein, inspired from the polypeptide ß-strand architecture, we have designed and developed novel bifacial π-conjugated polymers (M n: ca. 24 kDa) that are soluble (ca. 70 to >250 mM) despite the absence of pendant solubilizing chains. The impact of varying the bifacial monomer height on polymer solubility, optical properties, and interactions with small molecules is reported.

Aryl amphiphile shape-directors for shape-controlled synthesis of organic semiconductor particles.

Currently, shape- and size-controlled synthesis of organic micro- and nano-particles mostly relies on aliphatic amphiphiles, which lack the structural diversity to provide tunable amphiphile-particle facet interaction energies and result in a limited range of particle shapes. Herein we report the design, synthesis, and utilization of two novel aryl amphiphiles as shape-directors (ShaDs) to obtain particles of different shape. By changing the ShaDs aryl hydrophobe structure, 9,10-diphenylanthracene microcrystals of different shape were obtained with greater than 90% shape yield.

Macromolecular Design Strategies for Preventing Active-Material Crossover in Non-Aqueous All-Organic Redox-Flow Batteries.

Intermittent energy sources, including solar and wind, require scalable, low-cost, multi-hour energy storage solutions in order to be effectively incorporated into the grid. All-Organic non-aqueous redox-flow batteries offer a solution, but suffer from rapid capacity fade and low Coulombic efficiency due to the high permeability of redox-active species across the battery's membrane. Here we show that active-species crossover is arrested by scaling the membrane's pore size to molecular dimensions and in turn increasing the size of the active material above the membrane's pore-size exclusion limit. When oligomeric redox-active organics (RAOs) were paired with microporous polymer membranes, the rate of active-material crossover was reduced more than 9000-fold compared to traditional separators at minimal cost to ionic conductivity. This corresponds to an absolute rate of RAO crossover of less than 3 µmol cm-2 day-1 (for a 1.0 m concentration gradient), which exceeds performance targets recently set forth by the battery industry. This strategy was generalizable to both high and low-potential RAOs in a variety of non-aqueous electrolytes, highlighting the versatility of macromolecular design in implementing next-generation redox-flow batteries.