Effects of alkyl side chains positioning and presence of fused aromatic units in the backbone of low‐bandgap diketopyrrolopyrrole copolymers on the optoelectronic properties of organic solar cells

Chochos, Christos L.; Drakopoulou, Sofia; Miskaki, Christina; Krassas, Miron; Tzourmpakis, Pavlos; Kakavelakis, George; Sprau, Christian; Colsmann, Alexander; Squeo, Benedetta Maria; Gregoriou, Vasilis G.; Kymakis, Emmanuel; Avgeropoulos, Apostolos

doi:10.1002/pola.28901

Cited by 10 publications

(6 citation statements)

References 44 publications

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“…The polymers were synthesized via Stille coupling from a DPP-bithiophene monomer with each corresponding bithiophene ditin compound (see Materials and Methods). , In our previous study, it was found that the highly flexible thiophene-thiophene (T-T) dihedral in the isoindigo-bithiophene-based conjugated polymer is critical to forming wavy, helical polymer chain conformation. Such polymer chains further stack in a staggered fashion to form chiral helical fibrils in solution.…”

Section: Resultsmentioning

confidence: 99%

Subtle Molecular Changes Largely Modulate Chiral Helical Assemblies of Achiral Conjugated Polymers by Tuning Solution-State Aggregation

Park,

Luo,

Kwok

et al. 2023

ACS Cent. Sci.

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Understanding the solution-state aggregate structure and the consequent hierarchical assembly of conjugated polymers is crucial for controlling multiscale morphologies during solid thin-film deposition and the resultant electronic properties. However, it remains challenging to comprehend detailed solution aggregate structures of conjugated polymers, let alone their chiral assembly due to the complex aggregation behavior. Herein, we present solution-state aggregate structures and their impact on hierarchical chiral helical assembly using an achiral diketopyrrolopyrrole-quaterthiophene (DPP-T4) copolymer and its two close structural analogues wherein the bithiophene is functionalized with methyl groups (DPP-T2M2) or fluorine atoms (DPP-T2F2). Combining in-depth small-angle X-ray scattering analysis with various microscopic solution imaging techniques, we find distinct aggregate in each DPP solution: (i) semicrystalline 1D fiber aggregates of DPP-T2F2 with a strongly bound internal structure, (ii) semicrystalline 1D fiber aggregates of DPP-T2M2 with a weakly bound internal structure, and (iii) highly crystalline 2D sheet aggregates of DPP-T4. These nanoscopic aggregates develop into lyotropic chiral helical liquid crystal (LC) mesophases at high solution concentrations. Intriguingly, the dimensionality of solution aggregates largely modulates hierarchical chiral helical pitches across nanoscopic to micrometer scales, with the more rigid 2D sheet aggregate of DPP-T4 creating much larger pitch length than the more flexible 1D fiber aggregates. Combining relatively small helical pitch with long-range order, the striped twist-bent mesophase of DPP-T2F2 composed of highly ordered, more rigid 1D fiber aggregate exhibits an anisotropic dissymmetry factor (g-factor) as high as 0.09. This study can be a prominent addition to our knowledge on a solution-state hierarchical assembly of conjugated polymers and, in particular, chiral helical assembly of achiral organic semiconductors that can catalyze an emerging field of chiral (opto)electronics.

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Section: Resultsmentioning

confidence: 99%

Subtle Molecular Changes Largely Modulate Chiral Helical Assemblies of Achiral Conjugated Polymers by Tuning Solution-State Aggregation

Park,

Luo,

Kwok

et al. 2023

ACS Cent. Sci.

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“…3) the tail-to-tail connectivity has been reported to help increase the backbone planarity for DPP-based polymer in comparison with the head-to-head one. [51] This article is protected by copyright. All rights reserved.…”

Section: Resultsmentioning

confidence: 99%

“…chains. [51,54] This shallower HOMO is helpful for efficient doping because of the electron transfer between the polymers with polar side chains and the oxygen with low-lying LUMO energy level. [40] In order to get an insight into the structural and electronic properties of both polymers, we also performed the theoretical investigation and calculated the optimized This article is protected by copyright.…”

Section: Resultsmentioning

confidence: 99%

Triethylene Glycol Substituted Diketopyrrolopyrrole‐ and Isoindigo‐Dye Based Donor–Acceptor Copolymers for Organic Light‐Emitting Electrochemical Cells and Transistors

Liu

Kanahashi

Matsuki

et al. 2020

Adv Elect Materials

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Triethylene glycol (TEG), a common side chain, has been attached to two different dye moieties, diketopyrrolopyrrole (DPP) and isoindigo (II), and their bromo derivative monomers were copolymerized, respectively, with common bisstannyl alkylated bithiophene via Stille Coupling. The resulting donor-acceptor low-band-gap copolymers, namely, PTDPP-DT and PTII-DT are rationally deigned and synthesized conjugated polymeric systems suitable for doping. Both polymers were successfully investigated as singlecomponent and composite-system based electrochemical transistors (ECT) and light-emitting electrochemical cells (LEC) respectively. The PTDPP-DT thin film exhibits relatively high This article is protected by copyright. All rights reserved. electrical conductivity of up to 80 S cm -1 in the electrochemically doped state whereas PTII-DT thin film prevents the macroscopic charge transport due to a large-scale crystalline disorientation. Upon evaluating both polymers as an active conjugated material in the lightemitting electrochemical cells, they both exhibit emission under efficient electron/hole doping conditions.

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“…Functionalized aromatic systems bearing alkyl chains are important synthons for compounds with applications in materials science, − molecular electronics, − and catalysis . The self-assembly of organic or organometallic derivatives on metal surfaces often utilizes long alkyl chains, which ensure the alkyl-driven packing of self-assembled monolayers (SAMs) .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Long-Chain Alkanoyl Benzenes by an Aluminum(III) Chloride-Catalyzed Destannylative Acylation Reaction

2021

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This paper describes the facile synthesis of haloaryl compounds with long-chain alkanoyl substituents by the destannylative acylation of haloaryls bearing tri-n-butyltin (Bu 3 Sn) substituents. The method allows the synthesis of many important synthons for novel functional materials in a highly efficient manner. The halo-tri-n-butyltin benzenes are obtained by the lithium−halogen exchange of commercially available bis-haloarenes and the subsequent reaction with Bu 3 SnCl. Under typical Friedel−Crafts conditions, i.e., the presence of an acid chloride and AlCl 3 , the haloaryls are acylated through destannylation. The reactions proceed fast (<5 min) at low temperatures and thus are compatible with aromatic halogen substituents. Furthermore, the method is applicable to para-, meta-, and ortho-substitution and larger systems, as demonstrated for biphenyls. The generated tin byproducts were efficiently removed by trapping with silica/KF filtration, and most long-chain haloaryls were obtained chromatography-free. Molecular structures of several products were determined by X-ray single-crystal diffraction, and the crystal packing was investigated by mapping Hirshfeld surfaces onto individual molecules. A feasible reaction mechanism for the destannylative acylation reaction is proposed and supported through density functional theory (DFT) calculations. DFT results in combination with NMR-scale control experiments unambiguously demonstrate the importance of the tin substituent as a leaving group, which enables the acylation.

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Effects of alkyl side chains positioning and presence of fused aromatic units in the backbone of low‐bandgap diketopyrrolopyrrole copolymers on the optoelectronic properties of organic solar cells

Cited by 10 publications

References 44 publications

Subtle Molecular Changes Largely Modulate Chiral Helical Assemblies of Achiral Conjugated Polymers by Tuning Solution-State Aggregation

Subtle Molecular Changes Largely Modulate Chiral Helical Assemblies of Achiral Conjugated Polymers by Tuning Solution-State Aggregation

Triethylene Glycol Substituted Diketopyrrolopyrrole‐ and Isoindigo‐Dye Based Donor–Acceptor Copolymers for Organic Light‐Emitting Electrochemical Cells and Transistors

Synthesis of Long-Chain Alkanoyl Benzenes by an Aluminum(III) Chloride-Catalyzed Destannylative Acylation Reaction

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