S-Shaped Fused Azacorannulene Dimer: Structural and Redox Properties

Wang, Weifan; Hanindita, Fiona; Webster, Richard D.; Ito, Shingo

doi:10.31635/ccschem.022.202202165

Cited by 11 publications

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“…Our synthesis of pyridine-fused azacorannulenes 5 in Scheme adopts 1,3-dipolar cycloaddition of polycyclic aromatic azomethine ylides with a 1,2-diarylethyne followed by palladium-catalyzed intramolecular cyclization, which has been established as a powerful strategy for synthesizing curved buckybowls. ,, In this study, 1,2-dipyridylethyne was utilized as a dipolarophile to introduce pyridine rings. Thus, the 1,3-dipolar cycloaddition of alkyne 6 with the azomethine ylides generated from iminium salts 7 was performed.…”

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confidence: 99%

Pyridine-Fused Azacorannulene: Fine-Tuning of the Structure and Properties of Nitrogen-Embedded Buckybowls

Nakamura

Ochiai

Yubuta

et al. 2023

Precision Chemistry

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Heteroatom-embedded buckybowl molecules provide a fundamental molecular framework that has potential applications in various research fields. However, selective introduction of heteroatoms into buckybowls is challenging, and thus, studies investigating the effect of introduced heteroatoms have been limited. Here, we report the synthesis of pyridine-fused azacorannulene molecules. The influence of nitrogen atoms introduced into the peripheral positions on the structural, electronic, and optical properties is discussed.

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confidence: 99%

Pyridine-Fused Azacorannulene: Fine-Tuning of the Structure and Properties of Nitrogen-Embedded Buckybowls

Nakamura

Ochiai

Yubuta

et al. 2023

Precision Chemistry

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“…We also synthesized an S-Shaped fused azacorannulene dimer bearing a C62N2 π-surface using a smaller bifunctional azomethine ylide. 61 The product shows intriguing S shape in the crystal structure, as well as unique redox property. An open-shell radical cation and a close-shell di-radical di-cation with significantly different absorption/emission spectra are observed in the stepwise chemical oxidation of the product with different oxidants.…”

Section: Scheme 13 Synthesis Of Azapentabenzocorannulenementioning

confidence: 99%

Synthesis of nitrogen-containing polycyclic aromatic molecules by strain-enhanced 1,3-dipolar cycloaddition

Zhang¹

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Graphene and fullerenes are important carbon materials that have been intensively studied and widely applied in sensors, batteries, catalysts and many other areas. To expand the variety of these materials, doping of nitrogen atoms into carbon materials has become a common method. However, most reports on nitrogen-containing carbon materials utilize topdown synthesis, where the nitrogen substitution are not well-defined. To get a better control on the structures and properties of these materials, bottom-up approach with nitrogencontaining polycyclic aromatic molecules (NPAMs) as building blocks are essential.Although many NPAMs have been reported in recent years, the number of examples is still limited and their synthesis is usually complicated. Since 2015, our group has been focusing on synthesis of π-extended NPAMs via a highly reactive azomethine ylide. After a simple 1,3-dipolar cycloaddition and palladium-catalyzed cyclization procedure, NPAMs with large π-surface can be synthesized. However, the cycloaddition reaction is much less effective when applied on inactive unsaturated C-C bonds, such as the bonds with partially double bond character in pyrene or phenanthrene. In this work, we attempt to solve the problem by using strained substrates.Chapter 1 gives basic introduction and research background of this work. Top-down synthesis of nitrogen-containing carbon materials is briefly introduced, as well as its limitations, which leads to the necessity of bottom-up synthesis from NPAMs. Some representative NPAMs are listed, followed by those reported by our group via 1,3-dipolar cycloaddition with a highly reactive azomethine ylide. In this work, strained substrates are utilized in the cycloaddition, so molecular strain and strain-enhanced reactivity are also mentioned to give a strong support on our proposals.In Chapter 2, [7](2,7)pyrenophane, in which the pyrene moiety is bent by a highly strained alkylene chain, undergoes a strain-induced 1,3-dipolar cycloaddition and subsequent

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Spiro‐Buckybowls: Synthesis and Selective Transformations Toward Chiral and Nonlinear Optical Polycycles

Shang,

Wang,

Sun

et al. 2024

Angewandte Chemie

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Integration of spirocycles with buckybowls is a promising strategy to construct three‐dimensional (3D) curved π‐systems and to endow distinctive physicochemical features arising from buckybowls. Herein, a series of carbon‐bridged spiro‐type heterosumanenes (spiro‐HSEs) were synthesized by combining 9,9′‐spirobifluorene and dichalcogenasumanenes (DCSs). It is found that spiro‐conjugation plays an important role in the geometric and electronic structures of spiro‐HSEs. The bowl depth of DCSs moiety becomes larger in the spiro‐HSEs. Owing to the Jahn‐Teller (J‐T) effect, two DCSs segments of spiro‐HSEs have different bowl depths accompanied with the unequal distribution of charge in radical cation state. Taking advantage of the typical reactions of DCSs, selective transformations of spiro‐HSEs have been adopted in accordance to the nature of chalcogen atoms (S, Se, Te) to bestow the value‐added functionalities. The emissive property is enhanced by converting the thiophene rings of S‐doped spiro‐HSE into thiophene S,S‐dioxides. A chiroptical polycycle could be produced by ring‐opening of the edge benzene of Se‐doped spiro‐HSE. The covalent adduct of Te‐doped spiro‐HSE with Br2 forms non‐centrosymmetric halogen‐bonded networks, resulting in the high performance second‐order nonlinear optics (NLO).

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S-Shaped Fused Azacorannulene Dimer: Structural and Redox Properties

Cited by 11 publications

References 0 publications

Pyridine-Fused Azacorannulene: Fine-Tuning of the Structure and Properties of Nitrogen-Embedded Buckybowls

Pyridine-Fused Azacorannulene: Fine-Tuning of the Structure and Properties of Nitrogen-Embedded Buckybowls

Synthesis of nitrogen-containing polycyclic aromatic molecules by strain-enhanced 1,3-dipolar cycloaddition

Spiro‐Buckybowls: Synthesis and Selective Transformations Toward Chiral and Nonlinear Optical Polycycles

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