Lattice-Directed Formation of Covalent and Organometallic Molecular Wires by Terminal Alkynes on Ag Surfaces

Liu, Jing; Chen, Qiwei; Xiao, Li-Ye; Shang, Jian Ku; Zhou, Xiong; Zhang, Yajie; Wang, Yongfeng; Shao, Xiang; Li, Jianlong; Chen, Wei; Xu, Guo Qin; Tang, Hao; Zhao, Dahui; Wu, Kai

doi:10.1021/acsnano.5b01803

Cited by 125 publications

(144 citation statements)

References 62 publications

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“…The STM data ( Figure a) evidence polymeric wires of irregular shape resulting from a mixture of the targeted linear coupling (green circles) with twofold connections with varying bending angles (black) and a variety of threefold covalent linking motifs (red). Additionally, some connections with a sphere‐shaped protrusion between monomers (blue) are consistent with the expected geometry and appearance of Ag bis‐acetylides . Specifically, the large number of branched covalent connections obstructs the fabrication of linear, 1D nanowires with a precise structure.…”

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confidence: 54%

Functionalized Graphdiyne Nanowires: On‐Surface Synthesis and Assessment of Band Structure, Flexibility, and Information Storage Potential

Klappenberger

Hellwig

et al. 2018

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Carbon nanomaterials exhibit extraordinary mechanical and electronic properties desirable for future technologies. Beyond the popular sp -scaffolds, there is growing interest in their graphdiyne-related counterparts incorporating both sp and sp bonding in a regular scheme. Herein, we introduce carbonitrile-functionalized graphdiyne nanowires, as a novel conjugated, one-dimensional (1D) carbon nanomaterial systematically combining the virtues of covalent coupling and supramolecular concepts that are fabricated by on-surface synthesis. Specifically, a terphenylene backbone is extended with reactive terminal alkyne and polar carbonitrile (CN) moieties providing the required functionalities. It is demonstrated that the CN functionalization enables highly selective alkyne homocoupling forming polymer strands and gives rise to mutual lateral attraction entailing room-temperature stable double-stranded assemblies. By exploiting the templating effect of the vicinal Ag(455) surface, 40 nm long semiconducting nanowires are obtained and the first experimental assessment of their electronic band structure is achieved by angle-resolved photoemission spectroscopy indicating an effective mass below 0.1m for the top of the highest occupied band. Via molecular manipulation it is showcased that the novel oligomer exhibits extreme mechanical flexibility and opens unexplored ways of information encoding in clearly distinguishable CN-phenyl trans-cis species. Thus, conformational data storage with density of 0.36 bit nm and temperature stability beyond 150 K comes in reach.

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confidence: 54%

Functionalized Graphdiyne Nanowires: On‐Surface Synthesis and Assessment of Band Structure, Flexibility, and Information Storage Potential

Klappenberger

Hellwig

et al. 2018

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“…Sterically shielding the terminal alkyne functionalities was also applied by Wang, Zhao, Wu, and co‐workers to prepare linear, fully π‐conjugated polymeric chains . It is noteworthy that the authors observed along with the Glaser products, organometallic bisalkynylmetal species.…”

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

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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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“…[5][6][7][8][9] Thus on-surface synthesis demonstrates remarkable potential in the fabrication of novel nanostructures/nanomaterials that still remain challenging to be obtained by traditional synthetic methods.F or instance, carbon materials,i ncluding fullerenes,g raphene,g raphene nanoribbons,s ingle-chirality carbon nanotubes,a nd metalated carbyne,a sw ell as different hydrocarbons have been successfully fabricated by such on-surface synthetic strategies. [15][16][17][18][19] Thed emand for acetylenic scaffolds is due to the emergence of carbon nanostructures/nanomaterials,s uch as one-dimensional linear carbon (i.e., carbyne) and two-dimensional graphyne/ graphdiyne structures,w hich contain sp-hybridized carbon atoms.H owever,s cientific and technological advances made with these interesting carbon nanomaterials are significantly impeded by the high chemical activity of sp-hybridized carbon atoms.O n-surface CÀXb ond activation followed by aC ÀC coupling provides ar elatively efficient route to the synthesis of acetylenic linkages. [15][16][17][18][19] Thed emand for acetylenic scaffolds is due to the emergence of carbon nanostructures/nanomaterials,s uch as one-dimensional linear carbon (i.e., carbyne) and two-dimensional graphyne/ graphdiyne structures,w hich contain sp-hybridized carbon atoms.H owever,s cientific and technological advances made with these interesting carbon nanomaterials are significantly impeded by the high chemical activity of sp-hybridized carbon atoms.O n-surface CÀXb ond activation followed by aC ÀC coupling provides ar elatively efficient route to the synthesis of acetylenic linkages.…”

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confidence: 99%

“…[15][16][17][18][19] However,t he further functionalization of these molecular precursors with additional alkynyl groups to form carbon allotropes (e.g., graphdiyne) is hampered by the increasing instability of the precursors (e.g.,hexaethynylbenzene). [15][16][17][18][19] However,t he further functionalization of these molecular precursors with additional alkynyl groups to form carbon allotropes (e.g., graphdiyne) is hampered by the increasing instability of the precursors (e.g.,hexaethynylbenzene).…”

mentioning

confidence: 99%

Direct Formation of C−C Triple‐Bonded Structural Motifs by On‐Surface Dehalogenative Homocouplings of Tribromomethyl‐Substituted Arenes

Sun

Bao

et al. 2018

Angew Chem Int Ed

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On-surface synthesis shows significant potential in constructing novel nanostructures/nanomaterials, which has been intensely studied in recent years. The formation of acetylenic scaffolds provides an important route to the fabrication of emerging carbon nanostructures, including carbyne, graphyne, and graphdiyne, which feature chemically vulnerable sp-hybridized carbon atoms. Herein, we designed and synthesized a tribromomethyl-substituted compound. By using a combination of high-resolution scanning tunneling microscopy, non-contact atomic force microscopy, and density functional theory calculations, we demonstrated that it is feasible to convert these compounds directly into C-C triple-bonded structural motifs by on-surface dehalogenative homocoupling reactions. Concurrently, sp -hybridized carbon atoms are converted into sp-hybridized ones, that is, an alkyl group is transformed into an alkynyl moiety. Moreover, we achieved the formation of dimer structures, one-dimensional molecular wires, and two-dimensional molecular networks on Au(111) surfaces, which should inspire further studies towards two-dimensional graphyne structures.

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Lattice-Directed Formation of Covalent and Organometallic Molecular Wires by Terminal Alkynes on Ag Surfaces

Cited by 125 publications

References 62 publications

Functionalized Graphdiyne Nanowires: On‐Surface Synthesis and Assessment of Band Structure, Flexibility, and Information Storage Potential

Functionalized Graphdiyne Nanowires: On‐Surface Synthesis and Assessment of Band Structure, Flexibility, and Information Storage Potential

Covalent‐Bond Formation via On‐Surface Chemistry

Direct Formation of C−C Triple‐Bonded Structural Motifs by On‐Surface Dehalogenative Homocouplings of Tribromomethyl‐Substituted Arenes

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