Quasi one-dimensional band dispersion and surface metallization in long-range ordered polymeric wires

Vasseur, Guillaume; Fagot‐Revurat, Y.; Sicot, Muriel; Kierren, B.; Moreau, Luc; Malterre, D.; Cárdenas, Luis; Galeotti, Gianluca; Lipton‐Duffin, Josh; Rosei, Federico; Giovannantonio, Marco Di; Contini, G.; Fèvre, P. Le; Bertran, F.; Liang, Liangbo; Meunier, Vincent; Perepichka, Dmitrii F.

doi:10.1038/ncomms10235

Cited by 96 publications

(136 citation statements)

References 63 publications

Supporting

Mentioning

123

Contrasting

Unclassified

Order By: Relevance

“…In our STS measurements, we excluded networks with trapped halogens in the pores to avoid doping effects36. In addition, networks with a size less than seven rings and chains shorter than eight units were neglected to exclude an interfering size dependence35 in the measured electronic properties and to ensure maximum reproducibility.…”

Section: Resultsmentioning

confidence: 99%

Hierarchical on-surface synthesis and electronic structure of carbonyl-functionalized one- and two-dimensional covalent nanoarchitectures

et al. 2017

View full text Add to dashboard Cite

The fabrication of nanostructures in a bottom-up approach from specific molecular precursors offers the opportunity to create tailored materials for applications in nanoelectronics. However, the formation of defect-free two-dimensional (2D) covalent networks remains a challenge, which makes it difficult to unveil their electronic structure. Here we report on the hierarchical on-surface synthesis of nearly defect-free 2D covalent architectures with carbonyl-functionalized pores on Au(111), which is investigated by low-temperature scanning tunnelling microscopy in combination with density functional theory calculations. The carbonyl-bridged triphenylamine precursors form six-membered macrocycles and one-dimensional (1D) chains as intermediates in an Ullmann-type coupling reaction that are subsequently interlinked to 2D networks. The electronic band gap is narrowed when going from the monomer to 1D and 2D surface-confined π-conjugated organic polymers comprising the same building block. The significant drop of the electronic gap from the monomer to the polymer confirms an efficient conjugation along the triphenylamine units within the nanostructures.

show abstract

Section: Resultsmentioning

confidence: 99%

Hierarchical on-surface synthesis and electronic structure of carbonyl-functionalized one- and two-dimensional covalent nanoarchitectures

et al. 2017

View full text Add to dashboard Cite

show abstract

“…Therefore we believe that the fade of the loss structure at 2.1 eV confirms the polymerization upon annealing. Indeed, the decrease of the HOMO-LUMO gap is characteristic of the oligomerization of π -conjugated 1D or 2D organic systems37646566. Accordingly, the lowest excitation energies mainly from HOMO to LUMO evaluated by means of the time-dependent DFT (TD-DFT) method are 3.36, 1.98, 1.95, 1.93, and 1.92 eV for the monomer, dimer, trimer, tetramer and pentamer, respectively (see Supplementary Table 1 for a comparison of different functionals).…”

Section: Resultsmentioning

confidence: 99%

On-surface synthesis of aligned functional nanoribbons monitored by scanning tunnelling microscopy and vibrational spectroscopy

Kalashnyk

Mouhat

et al. 2017

Nat Commun

View full text Add to dashboard Cite

In the blooming field of on-surface synthesis, molecular building blocks are designed to self-assemble and covalently couple directly on a well-defined surface, thus allowing the exploration of unusual reaction pathways and the production of specific compounds in mild conditions. Here we report on the creation of functionalized organic nanoribbons on the Ag(110) surface. C–H bond activation and homo-coupling of the precursors is achieved upon thermal activation. The anisotropic substrate acts as an efficient template fostering the alignment of the nanoribbons, up to the full monolayer regime. The length of the nanoribbons can be sequentially increased by controlling the annealing temperature, from dimers to a maximum length of about 10 nm, limited by epitaxial stress. The different structures are characterized by room-temperature scanning tunnelling microscopy. Distinct signatures of the covalent coupling are measured with high-resolution electron energy loss spectroscopy, as supported by density functional theory calculations.

show abstract

“…This issue also affects the C=O related features in XPS: an overall broadening is observed for the O 1 s spectrum as well as for the high BE component of the C 1 s spectrum. An important expected effect of the polymerization would be the delocalization of the electronic states near the Fermi level . HREELS spectra were thus recorded for higher energy losses (see SI Figure S4) and indeed revealed a bathochromic effect, indicative of a reduction of the HOMO‐LUMO gap ,…”

Section: Figurementioning

confidence: 92%

The Orientation of Silver Surfaces Drives the Reactivity and the Selectivity in Homo‐Coupling Reactions

et al. 2018

View full text Add to dashboard Cite

Original reaction pathways can be explored in the on-surface synthesis approach where small aromatic precursors are confined to the surface of single crystal metals. The bis-indanedione molecule reacted with itself on silver surfaces in different ways, through a Knoevenagel reaction or an oxidative coupling, leading to the formation of a variety of new molecular compounds and covalently-linked 1D or 2D networks. Noteworthy, original reaction products were obtained that cannot be synthesized in traditional solvent-based chemistry. The lowest activation temperature for the homo-coupling reactions was found on the Ag(111) surface. The Ag(110) was highly selective in terms of coupling reaction type, while on Ag(100) the temperature could finely control the selectivity. The on-surface synthesis approach is shown here to be particularly efficient to produce original compounds in mild conditions, using activation temperatures as low as 200 °C. The different structures were characterized by scanning tunnelling microscopy (STM) together with X-ray photoelectron emission spectroscopy (XPS) and high-resolution electron energy loss spectroscopy (HREELS).

show abstract

Quasi one-dimensional band dispersion and surface metallization in long-range ordered polymeric wires

Cited by 96 publications

References 63 publications

Hierarchical on-surface synthesis and electronic structure of carbonyl-functionalized one- and two-dimensional covalent nanoarchitectures

Hierarchical on-surface synthesis and electronic structure of carbonyl-functionalized one- and two-dimensional covalent nanoarchitectures

On-surface synthesis of aligned functional nanoribbons monitored by scanning tunnelling microscopy and vibrational spectroscopy

The Orientation of Silver Surfaces Drives the Reactivity and the Selectivity in Homo‐Coupling Reactions

Contact Info

Product

Resources

About