One-step synthesis of polycyclic thianthrenes from unfunctionalized aromatics by thia-APEX reactions

Kawahara, Kou P; Ito, Hideto; Itami, Kenichiro

doi:10.1039/d2qo02058k

Cited by 5 publications

(6 citation statements)

References 110 publications

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“…In 2023, Ito, Itami, and Kawahara developed the same type of pseudo-thia-APEX reaction under mild reaction conditions. 40 Inspired by the previously developed thia-APEX reaction (Scheme 28 ), 37 S -diimidated arenedithiols 101 were designed as 1,2-phenylenedisulfonium ion equivalents. In the presence of 0.6 equiv of TfOH, stoichiometric pseudo-thia-APEX reactions of unfunctionalized arenes 100 with π-extending agents 101 efficiently proceeded to afford thianthrenes 102 in one step.…”

Section: Thia-apex Reactionsmentioning

confidence: 99%

“…Related to the thia-APEX reaction, pseudo-thia-APEX reactions that afford non-aromatic sulfur-containing polycyclic compounds in one step were also reported. [39][40][41] One early example by Sato in 1988 is related to a one-step construction of thianthrenes from benzene derivatives 97 in the presence of benzopentathiepin 98 and AlCl 3 (Scheme 27). 39 In the presence of AlCl 3 as a Lewis acid, 98 is thought to be electrophilically activated like a 1,2-phenylenedisulfonium ion to achieve the one-step annulative Friedel-Crafts reaction affording various thianthrenes 99.…”

Section: Pseudo-thia-apex Reaction Using Benzopentathiepin For the Co...mentioning

confidence: 99%

Section: Pseudo-thia-apex Reaction Affording -Extended Thianthrenes ...mentioning

confidence: 99%

“…Figure29 TfOH-catalyzed pseudo-thia-APEX reaction affording π-extended thianthrenes using S-diimidated arenedithiols 41. …”

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confidence: 99%

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Heteroatom-Embedding Annulative π-Extension (Hetero-APEX) Reactions: An Overview

Ito,

Itami,

Kawahara

2023

Synthesis

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Heteroatom-embedded polycyclic aromatic compounds (hetero-PACs) are a class of organic compounds contributing to a variety of research fields such as materials science, chemical biology and so on. For applications using hetero-PACs, efficient preparation of hetero-PACs is essential. In particular, reactions transforming unfunctionalized aromatic compounds to hetero-PACs using appropriate heteroatom-containing aromatic compounds (π-extending agents) represent the most ideal way to prepare hetero-PACs. In this review, such heteroatom-embedding annulative π-extension (hetero-APEX) reactions including their reaction mechanisms and scope of substrates are described.

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Section: Thia-apex Reactionsmentioning

confidence: 99%

Section: Pseudo-thia-apex Reaction Using Benzopentathiepin For the Co...mentioning

confidence: 99%

Section: Pseudo-thia-apex Reaction Affording -Extended Thianthrenes ...mentioning

confidence: 99%

“…Figure29 TfOH-catalyzed pseudo-thia-APEX reaction affording π-extended thianthrenes using S-diimidated arenedithiols 41. …”

mentioning

confidence: 99%

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Heteroatom-Embedding Annulative π-Extension (Hetero-APEX) Reactions: An Overview

Ito,

Itami,

Kawahara

2023

Synthesis

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“…7 Interestingly, in contrast to structurally closely related compounds, i.e., dioxines 9 or phenazines, 10 the dithiine unit is not planar with a C−S−C dihedral angle of 101°. In parallel to the dithiine-linked framework structure, also a model compound, benzo [5,6]- [1,4]dithiino [2,3-b]thianthrene-6,13-dicarbonitrile (bTEpCN), featuring two dithiine units, was isolated from the reaction of 2,3,5,6-tetrafluoroterephthalonitrile and benzene-1,2-dithiol, and the crystal structure could be solved with an angle of 120°between neighboring benzene rings (see Figure 1).…”

Section: ■ Introductionmentioning

confidence: 99%

Tuning the Planarity of an Aromatic Thianthrene-Based Molecule on Au(111)

Au-Yeung,

Sarkar,

Haldar

et al. 2024

J. Phys. Chem. C

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Nonplanar aromatic molecules are interesting systems for organic electronics and optoelectronics applications due to their high stability and electronic properties. By using scanning tunneling microscopy and spectroscopy, we investigated thianthrene-based molecules adsorbed on Au(111), which are nonplanar in the gas phase and the bulk solid state. Varying the molecular coverage leads to the formation of two different kinds of self-assembled structures: close-packed islands and quasione-dimensional chains. We found that the molecules are nonplanar within the close-packed islands, while the configuration is planar in the molecular chain and for single adsorbed molecules. Using vertical tip manipulation to isolate a molecule from the island, we demonstrate the conversion of a nonplanar molecule to its planar configuration. We discuss the two different geometries and their electronic properties with the support of density functional theory calculations.

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Nonplanar Nanographene: A Hydrocarbon Hole‐Transporting Material That Competes with Triarylamines

Morinaka,

Ito,

Fujimoto

et al. 2024

Angewandte Chemie

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Hole‐transporting materials (HTMs) are essential for optoelectronic devices, such as organic light‐emitting diodes (OLEDs), dye‐sensitized solar cells, and perovskite solar cells. Triarylamines have been employed as HTMs since they were introduced in 1987. However, heteroatoms or side chains embedded in the core skeleton of triarylamines can cause thermal and chemical stability problems. Herein, we report that hexabenzo[a,c,fg,j,l,op]tetracene (HBT), a small nonplanar nanographene, functions as a hydrocarbon HTM with hole transport properties that match those of triarylamine‐based HTMs. X‐ray structural analysis and theoretical calculations revealed effective multidirectional orbital interactions and transfer integrals for HBT. In‐depth experimental and theoretical analyses revealed that the nonplanarity‐inducing annulative π‐extension can achieve not only a stable amorphous state in bulk films, but also a higher increase in the highest occupied molecular orbital level than conventional linear or cyclic π‐extension. Furthermore, an in‐house manufactured HBT‐based OLED exhibited excellent performance, featuring superior curves for current density–voltage, external quantum efficiency–luminance, and lifetime compared to those of representative triarylamine‐based OLEDs. A notable improvement in device lifetime was observed for the HBT‐based OLED, highlighting the advantages of the hydrocarbon HTM. This study demonstrates the immense potential of small nonplanar nanographenes for optoelectronic device applications.

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One-step synthesis of polycyclic thianthrenes from unfunctionalized aromatics by thia-APEX reactions

Abstract: In this paper, thia-APEX reactions affording π-extended thianthrene derivatives from unfunctionalized aromatics are described. By utilizing S-diimidated 1,2-arenedithiols as benzene-1,2-dithiol dication synthons, new benzodithiine arms were fused to the unfunctionalized...

Cited by 5 publications

References 110 publications

Heteroatom-Embedding Annulative π-Extension (Hetero-APEX) Reactions: An Overview

Heteroatom-Embedding Annulative π-Extension (Hetero-APEX) Reactions: An Overview

Tuning the Planarity of an Aromatic Thianthrene-Based Molecule on Au(111)

Nonplanar Nanographene: A Hydrocarbon Hole‐Transporting Material That Competes with Triarylamines

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