In this article we discuss the synthesis of four new low band-gap co-polymers based on the diketopyrrolopyrrole (DPP) and benzotriazole (BTZ) monomer unit. We demonstrate that the BTZ unit allows for additional solubilizing side-chains on the co-monomer and show that the introduction of a linear side-chain on the DPP-unit leads to an increase in thin-film order and charge-carrier mobility if a sufficiently solubilizing, branched, side chain is attached to the BTZ. We compare two different synthetic routes, direct arylation and Suzuki-polycondensation, by a direct comparison of polymers obtained the two routes and show that direct arylation produces polymers with lower electrical performance which we attribute to a higher density of chain Furthermore we demonstrate that a polymer utilizing this design motif and synthesized Suzuki-polycondensation () exhibits exceptionally high and near balanced average electron and hole mobilities >2 cm V s which are among the highest, robustly extracted mobility values reported for DPP copolymers in a top-gate configuration to date. Our results demonstrate clearly that linear side chain substitution of the DPP unit together with co-monomers that allow for the use of sufficiently long or branched solubilizing side chains can be an attractive design motif for solution processable, high mobility DPP copolymers.
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http://dx.doi.org/10.1039/c5sc01326g | DOI Listing |
ACS Appl Mater Interfaces
January 2025
Department of Hydrogen and Renewable Energy, Kyungpook National University, Daegu 41566, Republic of Korea.
The side-chain directions in nonfullerene acceptors (NFAs) strongly influence the intermolecular interactions in NFAs; however, the influence of these side chains on the morphologies and charge carrier dynamics of Y6-based acceptors remains underexplored. In this study, we synthesize four distinct Y6-based acceptors, i.e.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing, Zhejiang 314001, China.
Asymmetric substitution is acknowledged as a straightforward yet potent approach for the optimization of small molecule acceptors (SMAs), thereby enhancing the power conversion efficiency (PCE) of organic solar cells (OSCs). In this work, we have successfully engineered and synthesized a novel asymmetric SMA, designated as Y6-R, which features a rhodanine-terminated inner side-chain. In devices with PM6 as the polymer donor, the asymmetric Y6-R demonstrated an impressive PCE of 18.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, Yanagido, Gifu 501-1193, Japan.
Control of the formation of liquid crystalline 3̄ gyroid phases and their nanostructures is critical to advance materials chemistry based on the structural feature of three-dimensional helical networks. Here, we present that introducing methyl side-group(s) and slight non-symmetry into aryloyl-hydrazine-based molecules is unexpectedly crucial for their formation and can be a new design strategy through tuning intermolecular interactions: the two chemical modifications in the core portion of the chain-core-chain type molecules effectively lower and extend the 3̄ phase temperature ranges with the increased twist angle between neighboring molecules along the network. The detailed analyses of the aggregation structure revealed the change in the core assembly mode from the double-layered core mode of the mother molecule (without methyl groups) to the single-layered core mode.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Chang Chun Institute of Applied Chemistry Chinese Academy of Sciences, Key Laboratory of Polymer Ecomaterials, 5625 Renmin Street, Changchun, , 130022, Changchun, CHINA.
Living cationic polymerization (LCP) is a classical technique for precision polymer synthesis; however, due to the high sensitivity of cationic active species towards chain-transfer/termination events, it is notoriously difficult to control polymerization under mild conditions, which inhibits its progress in advanced materials engineering. Here, we unlock a practical anion-binding catalytic strategy to address the historical dilemma in LCP. Our experimental and mechanistic studies demonstrate that commercially accessible hexafluoroisopropanol (HFIP), when used in high loading, can create higher-order HFIP aggregates to tame dormant-active species equilibrium via non-covalent anion-binding principle, in turn inducing distinctive polymerization kinetics behaviors that grant efficient chain propagation while minimizing competitive side reactions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
University of Wisconsin Madison, Chemistry, 1101 University Ave, 53706, Madison, UNITED STATES OF AMERICA.
Many applications of enzymes benefit from activity on structurally diverse substrates. Here, we sought to engineer the decarboxylative aldolase UstD to perform a challenging C-C bond forming reaction with ketone electrophiles. The parent enzyme had only low levels of activity, portending multiple rounds of directed evolution and a possibility that mutations may inadvertently increase the specificity of the enzyme for a single model screening substrate.
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