Insight into Organometallic Intermediate and Its Evolution to Covalent Bonding in Surface-Confined Ullmann Polymerization

Giovannantonio, Marco Di; Garah, Mohamed El; Lipton‐Duffin, Josh; Meunier, Vincent; Cárdenas, Luis; Revurat, Yannick Fagot; Cossaro, Albano; Verdini, Alberto; Perepichka, Dmitrii F.; Rosei, Federico; Contini, G.

doi:10.1021/nn4035684

Cited by 195 publications

(285 citation statements)

References 75 publications

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“…1), [46][47][48] recently identified as possible intermediates of the Ullmann coupling reaction. 46,49 Fig . 2a shows a STM image of the Cu(111) surface after DBBA deposition at 300 K. Molecular self-assembly gives rise to ordered zigzag-like chain structures, which can further coalesce into 2D islands.…”

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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“…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: 86%

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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“…Instead, C-C bonds were formed between the β-positions and C atoms of the phenyl rings after annealing to 573 K, indicating that also partial dehydrogenation of the phenyl rings occurred [489]. Note that C-C bond formation on the basis of surface-assisted dehalogenation of aromatic bromo-or iodocompounds (also referred to as Ullmann coupling) has also been studied with numerous non-porphyrinic compounds [485][486][487][488].…”

Section: Covalent Networkmentioning

confidence: 99%