On-Surface Synthesis of Unsaturated Carbon Nanostructures with Regularly Fused Pentagon–Heptagon Pairs

Hou, Ian Cheng-Yi; Sun, Qiang; Eimre, Kristjan; Giovannantonio, Marco Di; Urgel, José I.; Ruffieux, Pascal; Narita, Akimitsu; Fasel, Román; Müllen, Kläus

doi:10.1021/jacs.0c03635

Cited by 62 publications

(44 citation statements)

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“…[128] Most recently,N arita, Fasel, Müllen, and co-workers reported the surface-assisted synthesis of graphene nanoribbons with regularly fused pentagon-heptagon pairs (Scheme 41 d). [129] In this synthesis,t he Ullmann coupling of dibromo-biazulene provided organometallic polymer 1,1'biazulenyl-3,3'-diyls-Au( 165)b earing abundant C-Au-C and C-C linkages. [130] After further annealing of the sample at 250 8 8C, nc-AFM and STM images revealed the formation of dramatic curved nanostructures 166 and 167,d isplaying multiple fused pentagon-heptagon pairs.D espite the divergence in carbon skeleton exhibited in these two structures,in both cases the pentagons are located exclusively in the inner part of the curved structure,w ith the hexagons found on the outer edge and the heptagons embedded within.…”

Section: Methodsmentioning

confidence: 97%

Construction of Heptagon‐Containing Molecular Nanocarbons

et al. 2021

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Section: Methodsmentioning

confidence: 97%

Construction of Heptagon‐Containing Molecular Nanocarbons

et al. 2021

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“…Most recently, Narita, Fasel, Müllen, and co‐workers reported the surface‐assisted synthesis of graphene nanoribbons with regularly fused pentagon–heptagon pairs (Scheme 41 d). [129] In this synthesis, the Ullmann coupling of dibromo‐biazulene provided organometallic polymer 1,1′‐biazulenyl‐3,3′‐diyls‐Au ( 165 ) bearing abundant C‐Au‐C and C‐C linkages [130] . After further annealing of the sample at 250 °C, nc‐AFM and STM images revealed the formation of dramatic curved nanostructures 166 and 167 , displaying multiple fused pentagon–heptagon pairs.…”

Section: Surface‐assisted Synthesismentioning

confidence: 99%

Construction of Heptagon‐Containing Molecular Nanocarbons

et al. 2021

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Molecular nanocarbons containing heptagonal rings have attracted increasing interest due to their dynamic behavior, electronic properties, aromaticity, and solid‐state packing. Heptagon incorporation can not only induce negative curvature within nanocarbon scaffolds, but also confer significantly altered properties through interaction with adjacent non‐hexagonal rings. Despite the disclosure of several beautiful examples in recent years, synthetic strategies toward heptagon‐embedded molecular nanocarbons remain relatively limited due to the intrinsic challenges of heptagon formation and incorporation into polyarene frameworks. In this Review, recent advances in solution‐mediated and surface‐assisted synthesis of heptagon‐containing molecular nanocarbons, as well as the intriguing properties of these frameworks, will be discussed.

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“…In 2020, Hou et al. [ 99 ] reported the on‐surface synthesis of polycyclic sp 2 carbon nanostructures, which exhibited the multiple regular fusion of 5−7 pairs of azulene skeleton. As displayed in Figure a, biazulenyl was first synthesized from 1,3‐dibromoazulene under the Yamamoto conditions.…”

Section: Fused Azulenes and Nanoribbonsmentioning

confidence: 99%

Azulene‐Based Molecules, Polymers, and Frameworks for Optoelectronic and Energy Applications

Huang

Zhao

et al. 2020

Small Methods

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has a large dipole moment of 1.08 D. [2] By contrast, naphthalene, which only contains two fused six-membered rings, has a dipole moment of 0 D. Azulene, which was discovered and named by Piesse in 1863, has attracted considerable interest since its discovery in petroleum exploitation. [3] In 1937, Plattner and Pfau published their pioneering report on the synthesis of azulene. [4] However, their method was not practical due to its low azulene yield. In the 1950s, Ziegler and Hafner formulated a highly efficient and practical method for synthesizing azulene and its derivatives. [5] Because azulene is difficult to synthesize and has a low natural abundance, research on azulene-based molecules and materials is less advanced relative to research on its isomer. Direct functionalization of 1-and/ or 3-positions is a common and effective method of producing azulene derivatives. However, direct functionalization of other positions is much harder, e.g., bromination of 6-and 1,3-positions, [6] nucleophilic addition to obtain 6-subsituted azulene, [7] borylation at 2-position, [8] arylation at the 2-position, [9] and so on. The electron distribution in the front-line molecular orbitals (MOs) must usually be considered when functionalizing azulene. Because of resonance delocalization, the oddnumbered position of azulene, which is electron-rich, easily reacts with electrophilic compounds. Among the odd-numbered azulene varieties, 1-and 3-azulene have the highest activity. [10] By Azulene has a considerably larger dipole moment than its isomer naphthalene; it also has unique physicochemical properties, including different reactivities on five-and seven-membered rings, a dark color, a narrow gap between the highest occupied molecular orbital and lowest unoccupied molecular orbital, and stimulus response. Although azulene was discovered more than 100 years ago, the use of azulene-based derivatives can be traced back to five centuries ago. Due to its unusual structure, azulene-based molecules and materials are widely used in various fields. However, studies on azulene-based materials have long been hindered by difficulties in the synthesis. Considerably fewer studies have been conducted on azulene-based derivatives than on naphthalene-based derivatives. This perspective paper mainly introduces recent reports on the synthesis of azulene-based aromatic molecules, conjugated polymers, and coordination polymers, in addition to azulene-based frameworks. The structure-property relationship, optoelectronic applications, and energy-related applications of azulene-based derivatives are reviewed, including their use in near-infrared absorption, organic field-effect transistors, organic solar cells, and microsupercapacitors.

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On-Surface Synthesis of Unsaturated Carbon Nanostructures with Regularly Fused Pentagon–Heptagon Pairs

Cited by 62 publications

References 63 publications

Construction of Heptagon‐Containing Molecular Nanocarbons

Construction of Heptagon‐Containing Molecular Nanocarbons

Construction of Heptagon‐Containing Molecular Nanocarbons

Azulene‐Based Molecules, Polymers, and Frameworks for Optoelectronic and Energy Applications

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