Electronic structures of one-dimensional metal–molecule hybrid chains studied using scanning tunneling microscopy and density functional theory

Chung, Kyung Hoon; Koo, Bon Gil; Kim, Howon; Yoon, Jong Keon; Kim, Ji Hoon; Kwon, Young–Kyun; Kahng, Se-Jong

doi:10.1039/c2cp23295b

Cited by 50 publications

(69 citation statements)

References 32 publications

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“…The vision outlined above is in agreement with previous reports in which similarh alogenated molecules were dosed on metal surfaces [32] and is also supported by photoemission data (Figure 2).…”

Section: Resultssupporting

confidence: 92%

Control of the Intermolecular Coupling of Dibromotetracene on Cu(110) by the Sequential Activation of CBr and CH Bonds

Ferrighi

Píš

Nguyễn

et al. 2015

Chemistry A European J

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Dibromotetracene molecules are deposited on the Cu(110) surface at room temperature. The complex evolution of this system has been monitored at different temperatures (i.e., 298, 523, 673, and 723 K) by means of a variety of complementary techniques that range from STM and temperature-programmed desorption (TPD) to high-resolution X-ray spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). State-of-the-art density-functional calculations were used to determine the chemical processes that take place on the surface. After deposition at room temperature, the organic molecules are transformed into organometallic monomers through debromination and carbon-radical binding to copper adatoms. Organometallic dimers, trimers, or small oligomers, which present copper-bridged molecules, are formed by increasing the temperature. Surprisingly, further heating to 673 K causes the formation of elongated chains along the Cu(110) close-packed rows as a consequence of radical-site migration to the thermodynamically more stable molecule heads. Finally, massive dehydrogenation occurs at the highest temperature followed by ring condensation to nanographenic patches. This study is a paradigmatic example of how intermolecular coupling can be modulated by the stepwise control of a simple parameter, such as temperature, through a sequence of domino reactions.

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Section: Resultssupporting

confidence: 92%

Control of the Intermolecular Coupling of Dibromotetracene on Cu(110) by the Sequential Activation of CBr and CH Bonds

Ferrighi

Píš

Nguyễn

et al. 2015

Chemistry A European J

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“…These protrusions are reminiscent of features observed in the dehalogenation and polymerization of aryl-halides in 1D. 11,35,38 The dehalogenated molecules are stabilized by covalent bonds with silver surface atoms. This type of intermediate step in the reaction from the brominated molecule to polymer has been observed previously in the synthesis of porous graphene from iodo-substituted cyclohexa-m-phenylene on Ag(111).…”

Section: Cu (110) and Ag(110)mentioning

confidence: 78%

Ullmann-type coupling of brominated tetrathienoanthracene on copper and silver

et al. 2014

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We report the synthesis of extended two-dimensional organic networks on Cu(111), Ag(111), Cu(110), and Ag(110) from thiophene-based molecules. A combination of scanning tunnelling microscopy and X-ray photoemission spectroscopy yields insight into the reaction pathways from single molecules towards the formation of two-dimensional organometallic and polymeric structures via Ullmann reaction dehalogenation and C-C coupling. The thermal stability of the molecular networks is probed by annealing at elevated temperatures of up to 500 °C. On Cu(111) only organometallic structures are formed, while on Ag(111) both organometallic and covalent polymeric networks were found to coexist. The ratio between organometallic and covalent bonds could be controlled by means of the annealing temperature. The thiophene moieties start degrading at 200 °C on the copper surface, whereas on silver the degradation process becomes significant only at 400 °C. Our work reveals how the interplay of a specific surface type and temperature steers the formation of organometallic and polymeric networks and describes how these factors influence the structural integrity of two-dimensional organic networks.

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“…In addition, it was speculated that the terphenyl biradicals might pull out atoms from the surface, but this was not substantiated by further in-vestigations. [9] Pham et al recently compared the Ullmann coupling of tetrabromopyrene on Cu(111)a nd Au(111). [10] They found spontaneously formed CÀCuÀCb ridges in the former case (at 300 K), while halogen-mediatedi nteractions stabilized an on-covalently bound2 Dn etwork in the latter case.…”

Section: Introductionmentioning

confidence: 99%

Formation of Organometallic Intermediate States in On‐Surface Ullmann Couplings

Barton

Gao

Held

et al. 2017

Chemistry A European J

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Possible origins of the formation of organometallic intermediates in on-surface Ullmann couplings have been investigated by surface tunneling microscopy (STM) and density functional theory (DFT) calculations. We consider the case of iodobenzenes on the coinage metals copper, silver, and gold. We found experimental evidence for the formation of surface vacancies and the presence of metal adatoms in these coupling reactions, which are taken as a hint for the reactive extraction of surface atoms by adsorbates. In a second step, we demonstrate by ab initio molecular dynamics calculations for aryl-iodides on copper that metal atoms can be pulled out of the surface to form metal-organic species. By contrast, a thermally activated provision of a metal atom from the surface to form an adatom is energetically unfavorable. Finally, we investigate the mechanism and energetics of the reactive extraction of surface metal atoms by means of (climbing-image) nudged elastic band density-functional theory calculations for iodobenzene on copper, silver, and gold, and analyze our results in the light of the experimental findings.

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Electronic structures of one-dimensional metal–molecule hybrid chains studied using scanning tunneling microscopy and density functional theory

Cited by 50 publications

References 32 publications

Control of the Intermolecular Coupling of Dibromotetracene on Cu(110) by the Sequential Activation of CBr and CH Bonds

Control of the Intermolecular Coupling of Dibromotetracene on Cu(110) by the Sequential Activation of CBr and CH Bonds

Ullmann-type coupling of brominated tetrathienoanthracene on copper and silver

Formation of Organometallic Intermediate States in On‐Surface Ullmann Couplings

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