On-Surface Annulation Reaction Cascade for the Selective Synthesis of Diindenopyrene

Eisenhut, Frank; Lehmann, Thomas; Viertel, Andreas; Skidin, Dmitry; Krüger, Justus; Nikipar, Seddigheh; Ryndyk, Dmitry A.; Joachim, Christian; Hecht, Stefan; Moresco, Francesca; Cuniberti, Gianaurelio

doi:10.1021/acsnano.7b06459

Cited by 18 publications

(18 citation statements)

References 46 publications

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“…Organometallic chains are not the only possible reaction products. In fact, if new intermolecular C−C bonds cannot be achieved, the radical sites may also give rise to intramolecular C−C bond formation, as in the case of 4,10‐bis(2′‐bromo‐4′‐methylphenyl)‐1,3‐dimethylpyrene on Au(111) …”

Section: Introductionmentioning

confidence: 99%

Overcoming Steric Hindrance in Aryl‐Aryl Homocoupling via On‐Surface Copolymerization

et al. 2019

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On-surface synthesis is a unique tool for growing low-dimensional carbon nanomaterials with precise structural control down to the atomic level. This novel approach relies on carefully designed precursor molecules, which are deposited on suitable substrates and activated to ultimately form the desired nanostructures. One of the most applied reactions to covalently interlink molecular precursors is dehalogenative aryl-aryl coupling. Despite the versatility of this approach, many unsuccessful attempts are also known, most of them associated to the poor capability of the activated precursors to couple to each other. Such failure is often related to the steric hindrance between reactants, which may arise due to their coplanarity upon adsorption on a surface. Here, we propose a copolymerization approach to overcome the limitations that prevent intermolecular homocoupling. We apply the strategy of using suitable linkers as additional reactants to the formation of fully conjugated polycyclic nanowires incorporating non-benzenoid rings.

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Section: Introductionmentioning

confidence: 99%

Overcoming Steric Hindrance in Aryl‐Aryl Homocoupling via On‐Surface Copolymerization

et al. 2019

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“…4, 5, 7, 8) can be obtained by on-surface reactions of carefully designed precursors. [19][20][21][22][23] Notably, the implementation of azulene motifs containing 5 and 7-membered rings was demonstrated in nanographenes after the cyclodehydrogenation reaction. [24][25][26] Here, we describe the on-surface chemistry approach used to create atomically-defined 5-7 defects in nitrogen-doped nanographenes.…”

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confidence: 99%

On-surface synthesis of nitrogen-doped nanographenes with 5–7 membered rings

et al. 2019

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We report on the formation of nitrogen-doped nanographenes containing five-and seven-membered rings by thermally induced cyclodehydrogenation on the Au(111) surface. Using scanning tunneling microscopy and supported by calculations, we investigated the structure of precursor and targets, as well as of intermediates. Scanning tunneling spectroscopy shows that the electronic properties of the target nanographenes are strongly influenced by the additional formation of non-hexagonal rings.

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“…The ACID map also shows the clockwise direction of the main current ring on the P1 periphery revealing its aromatic character. Although in disagreement with 4n+2 rule of aromaticity, all πelectrons (28) are involved in this current. The aromaticity and, thus, the stabilization in the closedshell electronic structure are maintained by avoiding peripheral bonds of antiaromatic 4, 5-I and 5-III rings.…”

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confidence: 69%

“…From the chemical structure of the precursor and the products, we proposed a tentative course of reaction steps (see Scheme S1 and related discussion). P2 and P3 chemical structures have one carbon atom less than the precursor, suggesting a demethylation process upon their formation (28). On the other hand, P1, P4, and P5 products conserve the number of carbon atoms during the reaction course.…”

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confidence: 99%

On-Surface Mechanochemistry Synthesis of Non-Alternant Non-Benzenoid Aromatic Compounds Containing 4 to 8-Membered Rings

Mallada¹,

Mendieta‐Moreno²,

Nachtigalova³

et al. 2020

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Synthesis of polycyclic aromatic hydrocarbons containing various non-benzenoid rings remains a big challenge facing contemporary organic chemistry despite a considerable effort made over the last decades. Herein, we present a novel route, employing on-surface mechanochemistry, to synthesize non-alternant polycyclic aromatic hydrocarbon containing up to four distinct kinds of non-benzenoid rings. We show that the surface-induced mechanical constrains imposed on strained helical reactants play a decisive role leading to the formation of products, energetically unfavorable in solution, with a peculiar ring current stabilizing the aromatic character of the π-conjugated system. Determination of the chemical and electronic structures of the most frequent product reveals its closed-shell character and low band gap. The present study renders a new route for the synthesis of novel non-alternant polycyclic aromatic hydrocarbons or other hydrocarbons not available by traditional approaches of organic chemistry in solution.

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On-Surface Annulation Reaction Cascade for the Selective Synthesis of Diindenopyrene

Cited by 18 publications

References 46 publications

Overcoming Steric Hindrance in Aryl‐Aryl Homocoupling via On‐Surface Copolymerization

Overcoming Steric Hindrance in Aryl‐Aryl Homocoupling via On‐Surface Copolymerization

On-surface synthesis of nitrogen-doped nanographenes with 5–7 membered rings

On-Surface Mechanochemistry Synthesis of Non-Alternant Non-Benzenoid Aromatic Compounds Containing 4 to 8-Membered Rings

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