Closing the Nanographene Gap: Surface‐Assisted Synthesis of Peripentacene from 6,6′‐Bipentacene Precursors

Rogers, Christopher L.; Chen, Chen; Pedramrazi, Zahra; Omrani, Arash A.; Tsai, Hsin‐Zon; Jung, Han Sae; Lin, Song; Crommie, Michael F.; Fischer, Felix R.

doi:10.1002/anie.201507104

Cited by 132 publications

(109 citation statements)

References 41 publications

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“…The Scholl reaction, which is a well‐established dehydrogenative C−C coupling in solution‐phase chemistry, has been successfully conducted on an Au(111) surface by Crommie and Fischer . Intramolecular dehydrogenation of 6,6′‐bipentacene occurred at 200 °C, and the formation of the product peripentacene comprising four new C−C bonds was convincingly confirmed by STM as well as non‐contact AFM imaging at atomic resolution (Figure ).…”

Section: On‐surface C−h Activation Reactions For C−c Bond Formationmentioning

confidence: 87%

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Covalent‐Bond Formation via On‐Surface Chemistry

Held

Fuchs

Studer

2017

Chemistry A European J

146

134

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In this Review article pioneering work and recent achievements in the emerging research area of on-surface chemistry is discussed. On-surface chemistry, sometimes also called two-dimensional chemistry, shows great potential for bottom-up preparation of defined nanostructures. In contrast to traditional organic synthesis, where reactions are generally conducted in well-defined reaction flasks in solution, on-surface chemistry is performed in the cavity of a scanning probe microscope on a metal crystal under ultrahigh vacuum conditions. The metal first acts as a platform for self-assembly of the organic building blocks and in many cases it also acts as a catalyst for the given chemical transformation. Products and hence success of the reaction are directly analyzed by scanning probe microscopy. This Review provides a general overview of this chemistry highlighting advantages and disadvantages as compared to traditional reaction setups. The second part of the Review then focuses on reactions that have been successfully conducted as on-surface processes. On-surface Ullmann and Glaser couplings are addressed. In addition, cyclodehydrogenation reactions and cycloadditions are discussed and reactions involving the carbonyl functionality are highlighted. Finally, the first examples of sequential on-surface chemistry are considered in which two different functionalities are chemoselectively addressed. The Review gives an overview for experts working in the area but also offers a starting point to non-experts to enter into this exciting new interdisciplinary research field.

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Section: On‐surface C−h Activation Reactions For C−c Bond Formationmentioning

confidence: 87%

“… Intramolecular on‐surface Scholl reaction of bipentacene; a) STM image of 6,6′‐bipentacene; b) STM and nc AFM images of peripentacene . (Adapted with permission from ref.…”

Section: On‐surface C−h Activation Reactions For C−c Bond Formationmentioning

confidence: 99%

Covalent‐Bond Formation via On‐Surface Chemistry

Held

Fuchs

Studer

2017

Chemistry A European J

146

134

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“…An exemplary process of this type is the formation of tribenzo[a,g,m]coronene (215)f rom its molecular precursor 214 (Scheme 29). Research into the assembly of carbon-rich materials by an on-surface method was initiated by the synthesis of fullerene C 60 and its triaza-analogue, [250] hexabenzocoronene (138,R= H), [251] and other aromatic hemispheres [252] from compounds 138.S ince then, many challenging syntheses of carbon-based nanostructures have been realized by employing this approach, including single-chirality (that is,having one single chirality index (n,m)indicating the length and the direction of the circumventing vector) single-walled carbon nanotubes, [253] the longest to-date acenes [254] and periacenes, [255] PA Hs with embedded non-hexagonal rings, [256] and carbon-rich molecules with embedded nitrogen atoms. [169,250,257] An indisputable advantage of this method is the clear preference of the arene rings to undergo exclusively the desired cyclization that leads to the extended nanographenes and results in low-defect assemblies.…”

Section: Surface-assisted (Cyclo)dehydrogenation (Cdh)mentioning

confidence: 99%

Synthetic Applications of Oxidative Aromatic Coupling—From Biphenols to Nanographenes

et al. 2019

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Oxidative aromatic coupling occupies a fundamental place in the modern chemistry of aromatic compounds. It is a method of choice for the assembly of large and bewildering architectures. Considerable effort was also devoted to applications of the Scholl reaction for the synthesis of chiral biphenols and natural products. The ability to form biaryl linkages without any prefunctionalization provides an efficient pathway to many complex structures. Although the chemistry of this process is only now becoming fully understood, this reaction continues to both fascinate and challenge researchers. This is especially true for heterocoupling, that is, oxidative aromatic coupling with the chemoselective formation of a C−C bond between two different arenes. Analysis of the progress achieved in this field since 2013 reveals that many groups have contributed by pushing the boundary of structural possibilities, expanding into surface‐assisted (cyclo)dehydrogenation, and developing new reagents.

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“…On-Surface-Erhitzen zur Synthese von Molekülen Die zweite Mçglichkeit der On-Surface-Synthese ist die Erhitzung von molekularen Vorstufen, um Polymere und kovalent gebundene molekulare Netzwerke herzustellen. [24,75,88,[153][154][155][156] Ein jüngeres Beispiel gibt Abbildung 12. [147] Unlängst wurde die atomare Struktur von On-Surface-aufgebauten Graphen-Nanobändern durch AFM erfolgreich aufgeklärt, [148][149][150][151] siehe Abbildung 11.…”

Section: Manipulation Von Atomen Fürd Ie Molekülsyntheseunclassified

Rasterkraftmikroskopie für die molekulare Strukturaufklärung

et al. 2018

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Mit der Rastersondenmikroskopie kann man auf einer Oberfläche adsorbierte Moleküle individuell und mit hoher Auflösung untersuchen. Die Technik, die bei tiefen Temperaturen und im Ultrahochvakuum durchgeführt wird, liefert Informationen über Struktur, Konfiguration, Ladungszustand, Aromatizität und die Beteiligung von Resonanzstrukturen. Durch Funktionalisierung der Spitze eines Rasterkraftmikroskops mit einem CO‐Molekül können Einzelmoleküle mit atomarer Auflösung abgebildet werden, ihre Adsorptionsgeometrie kann gemessen und die Bindungsordnungen im Molekül können bestimmt werden. Mit der Rastertunnelmikroskopie und der Kelvinsondenkraftmikroskopie kann man zudem die Elektronendichte der molekularen Grenzorbitale bzw. die Ladungsverteilung innerhalb des Moleküls kartieren. In Kombination ergeben diese Methoden ein hochauflösendes Verfahren zur Identifizierung und Charakterisierung von Einzelmolekülen. Die Empfindlichkeit auf Einzelmoleküle sowie die Option, durch Manipulation von Atomen mit der Spitze des Mikroskops chemische Reaktionen auszulösen, eröffnen einzigartige chemische Anwendungsmöglichkeiten und heben die Rastersondenmikroskopie von den klassischen Methoden zur molekularen Strukturaufklärung heraus. Somit kann die Rasterkraftmikroskopie nicht nur bei der Identifizierung von schwer zu bestimmenden Naturstoffen helfen, sondern sie ist auch ein leistungsstarkes und besonders gut geeignetes Instrument, um Oberflächenreaktionen zu untersuchen und Radikale und molekulare Mischungen zu charakterisieren. In diesem Aufsatz zeigen wir auf, welche Entwicklung die hochauflösende Rastersondenmikroskopie mit funktionalisierter Spitze bei der molekularen Strukturaufklärung und ‐charakterisierung in den vergangenen Jahren genommen hat, und erörtern die Herausforderungen der kommenden Jahre.

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Closing the Nanographene Gap: Surface‐Assisted Synthesis of Peripentacene from 6,6′‐Bipentacene Precursors

Cited by 132 publications

References 41 publications

Covalent‐Bond Formation via On‐Surface Chemistry

Covalent‐Bond Formation via On‐Surface Chemistry

Synthetic Applications of Oxidative Aromatic Coupling—From Biphenols to Nanographenes

Rasterkraftmikroskopie für die molekulare Strukturaufklärung

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