Ullmann coupling of 2,7-dibromopyrene on Au(1 1 1) assisted by surface adatoms

Hu, Jiangang; Hu, Jielun; Zhang, Zhengde; Shen, Kongchao; Liang, Zhaofeng; Zhang, Huan; Tian, Qiwei; Wang, Peng; Jiang, Zheng; Huang, Han; Wells, Justin W.; Song, Fei

doi:10.1016/j.apsusc.2020.145797

Cited by 21 publications

(21 citation statements)

References 51 publications

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“…3b shows that 1D molecular chains are constructed in a well aligned manner that pyrene residues in neighbouring chains are directly facing to each other, while the pyrene frame is imaged as two non-identical bright protrusions. Besides, elongated dots are clearly resolved with the regular confinement between molecular chains, which can be assigned to liberated Br atoms from parent precursors after Ullmann-like coupling, as generally recognized in literature 18,37,45 . Meanwhile, the elongate shape of Br atoms might be related to the adsorption position (hollow site) with confinement in between linear chains on Bi(111)-Ag, causing the steric effect during STM imaging.…”

Section: Resultssupporting

confidence: 64%

Initiating Ullmann-like coupling of Br2Py by a semimetal surface

Wang

et al. 2021

Sci Rep

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Intensive efforts have been devoted to surface Ullmann-like coupling in recent years, due to its appealing success towards on-surface synthesis of tailor-made nanostructures. While attentions were mostly drawn on metallic substrates, however, Ullmann dehalogenation and coupling reaction on semimetal surfaces has been seldom addressed. Herein, we demonstrate the self-assembly of 2, 7-dibromopyrene (Br2Py) and the well controllable dehalogenation reaction of Br2Py on the Bi(111)–Ag substrate with a combination of scanning tunnelling microscopy (STM) and density functional theory calculations (DFT). By elaborately investigating the reaction path and formed organic nanostructures, it is revealed that the pristinely inert bismuth layer supported on the silver substrate can initiate Ullmann-like coupling in a desired manner by getting alloyed with Ag atoms underneath, while side products have not been discovered. By clarifying the pristine nature of Bi–Ag(111) and Ullmann-like reaction mechanisms, our report proposes an ideal template for thoroughly exploring dehalogenative coupling reaction mechanisms with atomic insights and on-surface synthesis of carbon-based architectures.

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Section: Resultssupporting

confidence: 64%

Initiating Ullmann-like coupling of Br2Py by a semimetal surface

Wang

et al. 2021

Sci Rep

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“…Upon deposition of 0.6 ML of DBP on Ag(110) at RT (bottom spectra in Figure 2ab), the Br 3d spectral region shows the presence of a major Br moiety evidenced by the 3d doublet with E b (Br 3d 5/2 )=68.2 eV and a minority one with E b (Br 3d 5/2 )=70.4 eV. The latter component is ascribed to Br-C bonds in the intact DBP molecules, as substantiated by comparison with the corresponding experiment performed at 1.2 ML DBP coverage 12 and by other experiments performed on the less reactive Au(111) surface 37,38 . The lower E b species corresponds, on the other hand, to Br atoms chemisorbed on the Ag substrate and its higher intensity indicates an almost complete debromination of the DBP admolecules at RT.…”

Section: I) Dbp/ag(110) At Rtsupporting

confidence: 67%

Morphological characterization and electronic properties of pristine and oxygen-exposed graphene nanoribbons on Ag(110)

Barcelon

Smerieri

Carraro

et al. 2021

Phys. Chem. Chem. Phys.

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“…Although the equilibrium concentration of adatoms on metal surfaces is expected to be small , on the order of 10 –9 on Cu and Ag around room temperaturedue to the high energy of their formation, such pre-existing adatoms have been known to form on copper, silver, and gold surfaces , near terrace edges and kinks. , These pre-existing adatoms have also been found to participate in metal organic coordination networks. − There is a growing body of evidence that adatoms can be created in the process of on-surface reactions. ,,− Quantifying the extent to which adatoms and other imperfections of the metal surface influence the thermodynamics and kinetics of the Ullmann coupling can inform new strategies for reaction optimization, leading, in turn, to better defect-free assembly of two-dimensional polymers.…”

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Adatoms in the Surface-Confined Ullmann Coupling of Phenyl Groups

Zhang

Perepichka

Khaliullin

2021

J. Phys. Chem. Lett.

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Despite the importance of the on-surface Ullmann coupling for synthesis of atomically precise carbon nanostructures, it is still unclear whether this reaction is catalyzed by surface atoms or adatoms. Here, the feasibility of the adatom creation and adatomcatalyzed Ullmann coupling of chloro-, bromo-, and iodobenzene on Cu(111), Ag(111), and Au(111) surfaces is examined using density functional theory modeling. The extraction of a metal atom is found to be greatly facilitated by the formation of strong phenyl−metal bonds, making the extraction energy barrier comparable to, and in the case of Ag(111) even lower than, that for the competing surfacecatalyzed phenyl−phenyl bond formation. However, if the phenyl− adatom bonds are too strong, as on Cu(111) and Ag(111), they create an insurmountable barrier for the subsequent adatom-catalyzed C−C coupling. In contrast, Au adatoms do not bind phenyl groups strongly and can catalyze the C−C bond formation almost as efficiently as surface atoms.

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Ullmann coupling of 2,7-dibromopyrene on Au(1 1 1) assisted by surface adatoms

Cited by 21 publications

References 51 publications

Initiating Ullmann-like coupling of Br2Py by a semimetal surface

Initiating Ullmann-like coupling of Br2Py by a semimetal surface

Morphological characterization and electronic properties of pristine and oxygen-exposed graphene nanoribbons on Ag(110)

Adatoms in the Surface-Confined Ullmann Coupling of Phenyl Groups

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