On-Surface Synthesis of a π-Extended Diaza[8]circulene

Nakamura, Kimihiro; Li, Qiang‐Qiang; Krejčí, Ondřej; Foster, Adam S.; Sun, Kewei; Kawai, Shigeki; Ito, Shingo

doi:10.1021/jacs.0c02534

“…In contrast to wet chemistry, the on‐surface reaction is free from the solubility issue and thus becomes of central importance to synthesize large polycyclic aromatic hydrocarbons (PAHs) such as graphene nanoribbons [29–31] . Furthermore, a large adsorption energy to the metal substrate induces planarization, leading to syntheses of unique PAHs, which are hardly obtained in solution [32] …”

Section: Figurementioning

confidence: 99%

Heterocyclic Ring‐Opening of Nanographene on Au(111)

Sun

¹

,

Sugawara

²

,

Lyalin

³

et al. 2021

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Cyclo‐dehydrogenation is of importance to induce the planarization of molecules on noble surfaces upon annealing. In contrast to a number of successful syntheses of polycyclic aromatic hydrocarbons by forming carbon–carbon bonds, it is still rare to conduct conjugation and cleavage of carbon–nitrogen bonds in molecules. Here, we present a systematic transformation of the C−N bonds in11,11,12,12‐tetraphenyl‐1,4,5,8‐tetraazaanthraquinodimethane as well as three other derivatives on Au(111). With bond‐resolved scanning tunneling microscopy, we discovered novel the “heterocyclic segregation” reaction of one pyrazine ring with two nitrogen atoms to form two quinoline rings with one nitrogen each. Density functional theory calculations showed that the intramolecular ring‐forming and ‐opening of N‐heterocycles are strongly affected by the initial hydrogen–substrate interaction.

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“…[29][30][31] Furthermore, a large adsorption energy to the metal substrate induces planarization, leading to syntheses of unique PAHs, which are hardly obtained in solution. [32] Here, we employed newly synthesized 11,11,12,12-tetraphenyl-1,4,5,8-tetraazaanthraquinodimethane 1 as well as three other derivatives as precursors. [33] The structures were directly identified with bond-resolved STM at 4.3 K. We found CÀN bond formations between pyrazine and phenyl groups after annealing at 370 K on Au(111).…”

mentioning

confidence: 99%

Heterocyclic Ring‐Opening of Nanographene on Au(111)

Sun

¹

,

Sugawara

²

,

Lyalin

³

et al. 2021

Self Cite

View full text Add to dashboard Cite

Cyclo‐dehydrogenation is of importance to induce the planarization of molecules on noble surfaces upon annealing. In contrast to a number of successful syntheses of polycyclic aromatic hydrocarbons by forming carbon–carbon bonds, it is still rare to conduct conjugation and cleavage of carbon–nitrogen bonds in molecules. Here, we present a systematic transformation of the C−N bonds in11,11,12,12‐tetraphenyl‐1,4,5,8‐tetraazaanthraquinodimethane as well as three other derivatives on Au(111). With bond‐resolved scanning tunneling microscopy, we discovered novel the “heterocyclic segregation” reaction of one pyrazine ring with two nitrogen atoms to form two quinoline rings with one nitrogen each. Density functional theory calculations showed that the intramolecular ring‐forming and ‐opening of N‐heterocycles are strongly affected by the initial hydrogen–substrate interaction.

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“…The demonstrated nanoarchitectonics strategy would be applied to the other units to produce various carbon nanostructures. Nakamura et al reported the synthesis of π-extended diaza [8]circulene through a combination of in-solution and on-surface syntheses (Figure 9) [79]. The final form of π-extended diaza [8]circulene possessing six hexagons and two pentagons cannot be obtained only with solution-based reaction processes.…”

Section: Atom/molecular-level Nanoarchitectonics Synthesismentioning

confidence: 99%

Progress in Molecular Nanoarchitectonics and Materials Nanoarchitectonics

Ariga

¹

2021

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Although various synthetic methodologies including organic synthesis, polymer chemistry, and materials science are the main contributors to the production of functional materials, the importance of regulation of nanoscale structures for better performance has become clear with recent science and technology developments. Therefore, a new research paradigm to produce functional material systems from nanoscale units has to be created as an advancement of nanoscale science. This task is assigned to an emerging concept, nanoarchitectonics, which aims to produce functional materials and functional structures from nanoscale unit components. This can be done through combining nanotechnology with the other research fields such as organic chemistry, supramolecular chemistry, materials science, and bio-related science. In this review article, the basic-level of nanoarchitectonics is first presented with atom/molecular-level structure formations and conversions from molecular units to functional materials. Then, two typical application-oriented nanoarchitectonics efforts in energy-oriented applications and bio-related applications are discussed. Finally, future directions of the molecular and materials nanoarchitectonics concepts for advancement of functional nanomaterials are briefly discussed.

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On-Surface Synthesis of a π-Extended Diaza[8]circulene

Cited by 38 publications

References 71 publications

Heterocyclic Ring‐Opening of Nanographene on Au(111)

Heterocyclic Ring‐Opening of Nanographene on Au(111)

Heterocyclic Ring‐Opening of Nanographene on Au(111)

Progress in Molecular Nanoarchitectonics and Materials Nanoarchitectonics

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