Substrate-controlled linking of molecular building blocks: Au(111) vs. Cu(111)

Koch, Matthias; Gille, Marie; Viertel, Andreas; Hecht, Stefan; Grill, Leonhard

doi:10.1016/j.susc.2014.04.011

Cited by 37 publications

(47 citation statements)

References 36 publications

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“…While on Au(111) covalent coupling is readily triggered after the radical generation, 44,45 for the case of similar molecules on Cu(111), metal adatoms have been shown to bind to the active C atoms, giving rise to C-Cu-C coordination (see Fig. 1), [46][47][48] recently identified as possible intermediates of the Ullmann coupling reaction. 46,49 Fig .…”

Section: Resultsmentioning

confidence: 99%

Imaging on-surface hierarchical assembly of chiral supramolecular networks

Patera

Zou

Dri

et al. 2017

Phys. Chem. Chem. Phys.

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The bottom-up assembly of chiral structures usually relies on a cascade of molecular recognition interactions. A thorough description of these complex stereochemical mechanisms requires the capability of imaging multilevel coordination in real-time. Here we report the first direct observation of hierarchical expression of supramolecular chirality at work, for 10,10 0 -dibromo-9,9 0 -bianthryl (DBBA) on Cu(111). Molecular recognition first steers the growth of chiral organometallic chains and then leads to the formation of enantiopure islands. The structure of the networks was determined by noncontact atomic force microscopy (nc-AFM), while high-speed scanning tunnelling microscopy (STM) revealed details of the assembly mechanisms at the ms time-scale. The direct observation of the chirality transfer pathways allowed us to evaluate the enantioselectivity of the interchain coupling.

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Section: Resultsmentioning

confidence: 99%

Imaging on-surface hierarchical assembly of chiral supramolecular networks

Patera

Zou

Dri

et al. 2017

Phys. Chem. Chem. Phys.

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“…In line with previous studies, we designed an on‐surface Ullmann coupling reaction (Figure ). Although the detailed chemical reaction path is unclear, the C–X (X = Br and I) σ bonds in such precursor molecules are cleaved on Ag, Au, and Cu surfaces . The reaction mechanism and its temperature depend on the reactivity of the substrate and the strength of the C–X σ bond.…”

Section: Resultsmentioning

confidence: 99%

Organometallic Bonding in an Ullmann-Type On-Surface Chemical Reaction Studied by High-Resolution Atomic Force Microscopy

Kawai

Sadeghi

Okamoto

et al. 2016

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The on-surface Ullmann-type chemical reaction synthesizes polymers by linking carbons of adjacent molecules on solid surfaces. Although an organometallic compound is recently identified as the reaction intermediate, little is known about the detailed structure of the bonded organometallic species and its influence on the molecule and the reaction. Herein atomic force microscopy at low temperature is used to study the reaction with 3,9-diiododinaphtho[2,3-b:2',3'-d]thiophene (I-DNT-VW), which is polymerized on Ag(111) in vacuum. Thermally sublimated I-DNT-VW picks up a Ag surface atom, forming a CAg bond at one end after removing an iodine. The CAg bond is usually short-lived, and a CAgC organometallic bond immediately forms with an adjacent molecule. The existence of the bonded Ag atoms strongly affects the bending angle and adsorption height of the molecular unit. Density functional theory calculations reveal the bending mechanism, which reveals that charge from the terminus of the molecule is transferred via the Ag atom into the organometallic bond and strengths the local adsorption to the substrate. Such deformations vanish when the Ag atoms are removed by annealing and CC bonds are established.

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“…Previous work on DBPM assemblies by Au{111} and Ag{111} 21 indicated that ideal substrates should be just reactive enough to lower the activation barriers of chemical reaction predetermined by the precursor molecular structure. 14,27,30,34,35 Our work shows that more reactive surfaces can be used to control the structure of the SAMA product, even dictating its symmetry. For example, the GNR-adsorption-chirality distribution is disperse over a Cu{111} terrace in Supporting Information Figure S9a.…”

Section: Conclusion and Prospectsmentioning

confidence: 85%

Bottom-Up Graphene-Nanoribbon Fabrication Reveals Chiral Edges and Enantioselectivity

et al. 2014

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We produce precise chiral-edge graphene nanoribbons on Cu{111} using self-assembly and surface-directed chemical reactions. We show that, using specific properties of the substrate, we can change the edge conformation of the nanoribbons, segregate their adsorption chiralities, and restrict their growth directions at low surface coverage. By elucidating the molecular-assembly mechanism, we demonstrate that our method constitutes an alternative bottom-up strategy toward synthesizing defect-free zigzag-edge graphene nanoribbons.

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Substrate-controlled linking of molecular building blocks: Au(111) vs. Cu(111)

Cited by 37 publications

References 36 publications

Imaging on-surface hierarchical assembly of chiral supramolecular networks

Imaging on-surface hierarchical assembly of chiral supramolecular networks

Organometallic Bonding in an Ullmann-Type On-Surface Chemical Reaction Studied by High-Resolution Atomic Force Microscopy

Bottom-Up Graphene-Nanoribbon Fabrication Reveals Chiral Edges and Enantioselectivity

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