Single-Molecule Resolution of an Organometallic Intermediate in a Surface-Supported Ullmann Coupling Reaction

Wang, Weihua; Shi, Xingqiang; Wang, Shiyong; Hove, M. A. Van; Lin, Nian

doi:10.1021/ja204956b

Cited by 289 publications

(378 citation statements)

References 29 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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“…Fig. 1(c)] in which the neighboring molecules are linked by C-Cu-C bonds, 28 denoted S3. The domain size of this structure is smaller than that of M1 or M2, presumably due to the fact that the stronger organometallic bonds restrict the development of large networks in the self-assembly process.…”

Section: Resultsmentioning

confidence: 99%

Tuning two-dimensional band structure of Cu(111) surface-state electrons that interplay with artificial supramolecular architectures

Wang

Tan

et al. 2013

Phys. Rev. B

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We report on the modulation of two-dimensional (2D) bands of Cu(111) surface-state electrons by three isostructural supramolecular honeycomb architectures with different periodicity or constituent molecules. Using Fourier-transformed scanning tunneling spectroscopy and model calculations, we resolved the 2D band structures and found that the intrinsic surface-state band is split into discrete bands. The band characteristics including band gap, band bottom, and bandwidth are controlled by the network unit cell size and the nature of the molecule-surface interaction. In particular, Dirac cones emerge where the second and third bands meet at the K points of the Brillouin zone of the supramolecular lattice.

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“…On the Cu(111) surface, debromination occurs at 300 K catalyzed by Cu adaoms and, at >470 K, polyphenylene (PP) oligomers are formed. [16][17][18] At higher annealing temperatures, in addition to the chainlike oligomers, many branched structures are present, as marked by the red circles in Fig. 1(a).…”

Section: Experiments and Calculationmentioning

confidence: 99%

Emergence of localized in-gap states in conjugated polymers of branched topology

Wang

Lin

2012

Phys. Rev. B

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Using cryogenic scanning tunneling microscopy and spectroscopy, we investigated cross-linked phenyelenebased polymers with various branched morphology at a single-molecule resolution. We found that localized states that are in the band gap of un-branched polymers emerge at the branch junctions. These in-gap states can be shifted close to the Fermi level through three means: extending the length of branch arms, coupling adjacent branches in hyperbranched structures, or increasing the number of branch arms. Single-band tight-binding calculations can reproduce all experimental results and provide quantitative relationships between the energy level shifts and the branching geometry. Our discovery evidences the emergence and development of in-gap states in the band structures of conjugated systems with fractional dimensions.

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Single-Molecule Resolution of an Organometallic Intermediate in a Surface-Supported Ullmann Coupling Reaction

Cited by 289 publications

References 29 publications

Imaging on-surface hierarchical assembly of chiral supramolecular networks

Imaging on-surface hierarchical assembly of chiral supramolecular networks

Tuning two-dimensional band structure of Cu(111) surface-state electrons that interplay with artificial supramolecular architectures

Emergence of localized in-gap states in conjugated polymers of branched topology

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