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Direct arylation polymerization (DArP) provides a more sustainable alternative to conventional methods for conjugated polymer synthesis, such as Stille–Migita or Suzuki–Miyura polymerizations. DArP proceeds through a C–H activation pathway, allowing for a reduction in the synthetic steps needed to access the monomer, since the installation of a transmetallating reagent, such as an organostannane or organoboron, is not required. However, compared to small-molecule synthesis, the prevalent conditions employed for DArP still require hazardous or unsustainably sourced reaction components, such as the solvent and transition-metal catalyst. This mini-review highlights recent work on the implementation of sustainable solvents, transition metal catalysts, and overall polymerization methods for DArP. The extension of small-molecule direct arylation conditions towards polymer synthesis is also discussed, along with the associated challenges, mechanistic considerations, and outlook for future work.
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Room-temperature Pd/Ag direct arylation enabled by a radical pathway
Direct arylation is an appealing method for preparing π-conjugated materials, avoiding the prefunctionalization required for traditional cross-coupling methods. A major effort in organic electronic materials development is improving the environmental and economic impact of production; direct arylation polymerization (DArP) is an effective method to achieve these goals. Room-temperature polymerization would further improve the cost and energy efficiencies required to prepare these materials. Reported herein is new mechanistic work studying the underlying mechanism of room temperature direct arylation between iodobenzene and indole. Results indicate that room-temperature, Pd/Ag-catalyzed direct arylation systems are radical-mediated. This is in contrast to the commonly proposed two-electron mechanisms for direct arylation and appears to extend to other substrates such as benzo[ b ]thiophene and pentafluorobenzene.
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- Award ID(s):
- 1700982
- PAR ID:
- 10170971
- Date Published:
- Journal Name:
- Beilstein Journal of Organic Chemistry
- Volume:
- 16
- ISSN:
- 1860-5397
- Page Range / eLocation ID:
- 384 to 390
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract In the past decade, direct arylation polymerization (DArP) has rapidly developed as a sustainable synthetic protocol for cost‐effective, atom‐economical preparation of conjugated polymers. By circumventing monomer functionalization with toxic transmetallating reagents such as organostannane and organoboron required for Stille‐Migita and Suzuki‐Miyaura polymerization methods, DArP proceeds through a metal‐catalyzed CH activation pathway for the preparation of high‐performance conjugated polymer materials. This review evaluates the development of several classes of efficient catalysts/catalytic systems from small‐molecule studies to polymerizations, including the mechanisms involved in these transformations and how they inspire catalyst and monomer design for defect‐free conjugated polymer synthesis. Recent advances in developing more sustainable first‐row transition metal catalysts for DArP are also highlighted, and the fundamental understanding of these efficient and sustainable catalysts should motivate the pursuit for the next generation of catalytic design to enable more effective and environmentally friendly conjugated polymer synthesis.more » « less
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Initial reports on the novel Cu-catalyzed direct arylation polymerization (Cu-DArP) stated that it required the use of aryl iodides. Herein, we report the first Cu-DArP methodology using more accessible and practical aryl-bromides with catalytic Cu, leading to a range of conjugated polymers with good molecular weights (up to 17.3 kDa) and an undetectable level of defects.more » « less
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An alkyl-substituted indacenodithiophene-based donor–acceptor π-conjugated polymer ( PIDTBPD ) with low stiffness and high ductility is reported. The polymer was synthesized after DFT calculations predicted that it would have a kinked backbone conformation while showing strong intramolecular charge transfer (ICT), suggestive of the fact that it would be beneficial to the polymer's elasticity and charge mobility. Atom-efficient direct arylation polymerization (DArP) was exploited to synthesize the polymer. Mechanical studies indicate that PIDTBPD has relatively rapid stress-relaxation properties, which lead to a low elastic modulus of 200 MPa and high crack-onset strain of ca . 40% (lower limit). A moderate charge carrier mobility of 2 × 10 −3 cm 2 V −1 s −1 with a current on/off ratio of 2.5 × 10 6 was obtained from the fabricated OFETs. Further experiments were performed to elucidate the structural aspects of this polymer: UV-Vis and PL spectra suggest that minimal conformational change occurs in the polymer between its diluted solution and thin film states; DSC measurements indicate that the polymer's T g is below −20 °C, allowing it to be in a rubbery state at room temperature; and XRD studies support this observation suggesting that the polymer is mostly amorphous at room temperature.more » « less
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Conjugated copolymers containing electron donor and acceptor units in their main chain have emerged as promising materials for organic electronic devices due to their tunable optoelectronic properties. Herein, we describe the use of direct arylation polymerization to create a series of fully π-conjugated copolymers containing the highly tailorable purine scaffold as a key design element. To create efficient coupling sites, dihalopurines are flanked by alkylthiophenes to create a monomer that is readily copolymerized with a variety of conjugated comonomers, ranging from electron-donating 3,4-dihydro-2 H -thieno[3,4- b ][1,4]dioxepine to electron-accepting 4,7-bis(5-bromo-3-hexylthiophen-2-yl)benzo[ c ][1,2,5]thiadiazole. The comonomer choice and electronic nature of the purine scaffold allow the photophysical properties of the purine-containing copolymers to be widely varied, with optical bandgaps ranging from 1.96–2.46 eV, and photoluminescent quantum yields as high as ϕ = 0.61. Frontier orbital energy levels determined for the various copolymers using density functional theory tight binding calculations track with experimental results, and the geometric structures of the alkylthiophene-flanked purine monomer and its copolymer are found to be nearly planar. The utility of direct arylation polymerization and intrinsic tailorability of the purine scaffold highlight the potential of these fully conjugated polymers to establish structure–property relationships based on connectivity pattern and comonomer type, which may broadly inform efforts to advance purine-containing conjugated copolymers for various applications.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3762/bjoc.16.36
