Pd-Free synthesis of dithienothiophene-based oligoaryls for effective hole-transporting materials by optimized Cu-catalyzed annulation and direct C–H arylation

Tu, Chen-Hsin; Wu, Ming‐Chung; Chen, Jui-Heng; Chiang, Chia-Hua; Hsu, Shen-Chieh; Hsu, Ming‐Wei; Liu, Ching Yuan

doi:10.1039/d2qo00187j

Cited by 5 publications

(2 citation statements)

References 38 publications

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“…Liu and co-workers [41] synthesized dithienothiophene oligoaryl derivatives using copper catalyst for direct acylation via CÀ H/CÀ I activation. Dual CÀ C coupling was done utilizing CuI as catalyst, K 3 PO 4 in N, N-dimethylpropyleneurea (DMPU) at 130 to 160 °C to give optimum yields.…”

Section: Aryl(sp 2 )-Aryl(sp 2 ) Bond Formationmentioning

confidence: 99%

Copper‐Catalyzed C(sp²)−C(sp²) Bond Formation via Single C(sp²)−H Activation

Parmar,

Adodariya,

Patel

et al. 2024

ChemistrySelect

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This review provides a comprehensive overview and evaluation of the studies conducted over the past 15 years into copper catalyzed reactions for C(sp2)−C(sp2) bond formation via C(sp2)−H activation. The investigations encompass a wide array of starting materials and substrates. The range of substrates studied has been broadened to encompass C−H activation of aryls, heteroaryls, and alkenyl groups. Furthermore, in some cases only catalytic amounts of copper salts were required to drive the challenging C−H functionalization, indicating a promising avenue for future research.

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Section: Aryl(sp 2 )-Aryl(sp 2 ) Bond Formationmentioning

confidence: 99%

Copper‐Catalyzed C(sp²)−C(sp²) Bond Formation via Single C(sp²)−H Activation

Parmar,

Adodariya,

Patel

et al. 2024

ChemistrySelect

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“…As shown in Table , we achieved exceptional yields of 99% and only 1% of structural defects with no evidence of β-defect at a retention time of 10.34–10.38 min. We have investigated the effects of an aromatic nitrogen ligand (1,10-phenantroline) which has often been used as a ligand for copper-catalyzed direct arylation. − Although we achieved a good yield (93%), we observed 6% structural defects (Table ).…”

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confidence: 95%

Direct Heteroarylation Guidelines for Well-Defined Thiophene-Based Conjugated Molecules

2023

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Direct (hetero)arylation polymerization (DHAP) shows great promise for simple, low cost, and benign preparation of conjugated polymers. However, coupling selectivity has always posed a problem. Herein, direct (hetero)arylation was studied on small molecule models to develop suitable conditions for C–C couplings between 2-methylthiophene acting as an electron-donating moiety and 2-thiophenecarbonitrile acting as an electron-withdrawing moiety, when one of the partners is brominated. We observed that the best conditions are obtained when the electron-withdrawing moiety is halogenated.

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New Molecular Design, Step‐Saving Synthesis, and Applications of Indolocarbazole Core‐Based Oligo(hetero)arenes

Lin,

Chiu,

Cao

et al. 2023

Chemistry An Asian Journal

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In this work, we have successfully synthesized 15 new examples (LLA01‐06; LinLi01‐10) of small‐molecule hole‐transporting materials (HTM) using the less explored indolocarbazole (ICbz) as core moiety. Different from previously reported ICbz HTMs, LinLi01‐10 exhibit new molecular designs in which 3,4‐ethylenedioxythiophene (EDOT) units are inserted as crucial π‐spacers and fluorine atoms are introdcued into end‐group molecules. These substantially improve the materials solubility and device power conversion efficiencies (PCEs) while fabricated in perovskite solar cells (PSC). More importantly, LinLi01‐10 are generated by a sustainable synthetic approach involving the use of straightforward C−H/C−Br couplings as key transformations, thus avoiding additional synthetic transformations including halogenation and borylation reactions called substrate prefunctionalizations usually required in Suzuki reactions. Most HTM molecules can be purified simply by reprecipitations instead of conducting column chromatography. In contrast to LLA01‐06 without additional EDOT moieties, PSC devices using LinLi01‐10 as hole‐transport layers display promising PCEs of up to 17.5 %. Interestingly, PSC devices employing seven of the LinLi01‐10 as hole‐transport molecules, respectively, are all able to show an immediate >10 % PCE (t=0) without any device oxidation/aging process that is necessary for the commercial spiro‐OMeTAD based PSCs.

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Pd-Free synthesis of dithienothiophene-based oligoaryls for effective hole-transporting materials by optimized Cu-catalyzed annulation and direct C–H arylation

Abstract: For the first time, [Cu]-catalyzed annulation and direct C–H/C–I couplings were used as key transformations to access new DTT-based hole-transporting materials (HTMs), CHC05–07. Perovskite solar cells with CHC07 display PCEs of up to 14.7%.

Cited by 5 publications

References 38 publications

Copper‐Catalyzed C(sp²)−C(sp²) Bond Formation via Single C(sp²)−H Activation

Copper‐Catalyzed C(sp²)−C(sp²) Bond Formation via Single C(sp²)−H Activation

Direct Heteroarylation Guidelines for Well-Defined Thiophene-Based Conjugated Molecules

New Molecular Design, Step‐Saving Synthesis, and Applications of Indolocarbazole Core‐Based Oligo(hetero)arenes

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Pd-Free synthesis of dithienothiophene-based oligoaryls for effective hole-transporting materials by optimized Cu-catalyzed annulation and direct C–H arylation

Abstract: For the first time, [Cu]-catalyzed annulation and direct C–H/C–I couplings were used as key transformations to access new DTT-based hole-transporting materials (HTMs), CHC05–07. Perovskite solar cells with CHC07 display PCEs of up to 14.7%.

Cited by 5 publications

References 38 publications

Copper‐Catalyzed C(sp2)−C(sp2) Bond Formation via Single C(sp2)−H Activation

Copper‐Catalyzed C(sp2)−C(sp2) Bond Formation via Single C(sp2)−H Activation

Direct Heteroarylation Guidelines for Well-Defined Thiophene-Based Conjugated Molecules

New Molecular Design, Step‐Saving Synthesis, and Applications of Indolocarbazole Core‐Based Oligo(hetero)arenes

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Product

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Copper‐Catalyzed C(sp²)−C(sp²) Bond Formation via Single C(sp²)−H Activation

Copper‐Catalyzed C(sp²)−C(sp²) Bond Formation via Single C(sp²)−H Activation