An 80-Carbon Aromatic Saddle Enabled by a Naphthalene-Directed Scholl Reaction

Pun, Sai Ho; Chan, Chi Kit; Liu, Zhifeng; Miao, Qian

doi:10.1055/s-0040-1716499

Cited by 15 publications

(7 citation statements)

References 22 publications

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“…Carbon schwarzites are a long-sought-after target in carbon nanoscience but have not been synthesized unambiguously yet. , Interesting properties and potential applications of carbon schwarzites are predicted on the basis of computational studies. , First-principles calculations suggest potential application of carbon schwarzites in lithium ion batteries as new anode materials, where the negatively curved surface binds lithium ions with higher affinity than a flat surface and the presence of pores enable three-dimensional lithium ion diffusion paths with relatively small energy barriers. Fragments that contain key structural information on carbon schwarzites are negatively curved nanographenes, − which have polycyclic aromatic frameworks containing seven-, − eight-membered − or larger rings. They are proposed as templates or monomers in synthesis of carbon schwarzites in a bottom-up approach. ,, …”

Section: Introductionmentioning

confidence: 99%

Charging a Negatively Curved Nanographene and Its Covalent Network

et al. 2021

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This study explores a bottom-up approach toward negatively curved carbon allotropes from octabenzo[8]circulene, a negatively curved nanographene. Stepwise chemical reduction reactions of octabenzo[8]circulene with alkali metals lead to a unique highly reduced hydrocarbon pentaanion, which is revealed by X-ray crystallography suggesting a local view for the reduction and alkali metal intercalation processes of negatively curved carbon allotropes. Polymerization of the tetrabromo derivative of octabenzo[8]circulene by the nickel-mediated Yamamoto coupling reaction results in a new type of porous carbon-rich material, which consists of a covalent network of negatively curved nanographenes. It has a specific surface area of 732 m2 g–1 and functions as anode material for lithium ion batteries exhibiting a maximum capacity of 830 mAh·g–1 at a current density of 100 mA·g–1. These results indicate that this covalent network presents the key structural and functional features of negatively curved carbon allotropes.

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Section: Introductionmentioning

confidence: 99%

Charging a Negatively Curved Nanographene and Its Covalent Network

et al. 2021

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“…Tobe and Yamada also observed contraction of an eight-membered ring under a condition for the Scholl reaction. The rearrangement in the Scholl reaction of 196 can be avoided by replacing two benzene rings in the teraphenylene unit with naphthalene rings, as demonstrated by the successful synthesis of 199 , an aromatic saddle composed of 80 sp 2 carbons, by Miao and co-workers in 2020 . As shown in Scheme b, oxidation of the naphthalene-containing precursor ( 198 ) with DDQ (11 equiv)/CF 3 SO 3 H gave 199 in a yield of 38% with formation of 10 C–C bonds.…”

Section: Rearrangement In Synthesis Of Curved Polycyclic Aromatics Th...mentioning

confidence: 93%

The Scholl Reaction as a Powerful Tool for Synthesis of Curved Polycyclic Aromatics

2022

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The past decade has witnessed remarkable success in the synthesis of curved polycyclic aromatics through Scholl reactions which enable oxidative aryl–aryl coupling even in company with the introduction of significant steric strain. These curved polycyclic aromatics are not only unique objects of structural organic chemistry in relation to the nature of aromaticity but also play an important role in bottom-up approaches to precise synthesis of nanocarbons of unique topology. Moreover, they have received considerable attention in the fields of supramolecular chemistry and organic functional materials because of their interesting properties and promising applications. Despite the great success of Scholl reactions in synthesis of curved polycyclic aromatics, the outcome of a newly designed substrate in the Scholl reaction still cannot be predicted in a generic and precise manner largely due to limited understanding on the reaction mechanism and possible rearrangement processes. This review provides an overview of Scholl reactions with a focus on their applications in synthesis of curved polycyclic aromatics with interesting structures and properties and aims to shed light on the key factors that affect Scholl reactions in synthesizing sterically strained polycyclic aromatics.

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“…The robustness of this method was further confirmed by Miao and coworkers with the synthesis of an octagon-embedded aromatic saddle consisting of 80 sp 2 carbons (Scheme 24). 100 The formation of ten new aryl–aryl bonds in making 88 was achieved in a straightforward manner using 11 equivalents of DDQ, but a stepwise formation is also possible. This alternative employed 4.5 equivalents of DDQ to form first the four new C–C bonds needed to create the [8]circulene core of 87 , and subsequent use of 7 equivalents of oxidant closed the framework with six additional new C–C bonds with comparable yield results to the single-step reaction.…”

Section: Synthesis Of Building Blocksmentioning

confidence: 99%