On-Surface Synthesis and Characterization of Honeycombene Oligophenylene Macrocycles

Chen, Min; Shang, Jian Ku; Wang, Yongfeng; Wu, Kai; Kuttner, Julian; Hilt, Gerhard; Hieringer, Wolfgang; Gottfried, J. Michael

doi:10.1021/acsnano.6b05709

Cited by 39 publications

(38 citation statements)

References 82 publications

(158 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However these highly mobile features are difficult to image. Similar structures have been observed previously on ( ) metal surfaces 11 , 32 . The study on a silver surface however was performed at 78 K or lower, suggesting that there may be more hexagonal structures on the surface, but they are diffusing too rapidly to be observed at room temperature.…”

Section: Resultssupporting

confidence: 89%

Ullmann Coupling Reactions on Ag(111) and Ag(110); Substrate Influence on the Formation of Covalently Coupled Products and Intermediate Metal-Organic Structures

Judd

Haddow

Champness

et al. 2017

Sci Rep

View full text Add to dashboard Cite

On-surface reactions based on Ullmann coupling are known to proceed on coinage-metal substrates (e.g. Au, Ag, Cu), with the chemistry of the surface strongly influencing the reaction progression. In addition, the topography of the surface may be expected to affect the local adsorption geometry of the reactants as well as the intermediate and final structures. Here, we investigate the effect of two different surface facets of silver, Ag(111) and Ag(110) on the formation of organometallic and covalent structures for Ullmann-type coupling reactions. Deposition of 4,4”-diiodo-m-terphenyl molecules onto either Ag(111) or Ag(110) surfaces leads to the scission of C-I bonds followed by the formation of organometallic zigzag structures, consisting of molecules connected by coordination bonds to Ag adatoms. The covalently coupled product is formed by annealing each surface, leading to the removal of Ag atoms and the formation of covalently bonded zigzag poly(m-phenylene) structures. Comparisons of the adsorption model of molecules on each surface before and after annealing reveal that on Ag(111), structures rearrange by rotation and elongation of bonds in order to become commensurate with the surface, whereas for the Ag(110) surface, the similarity in adsorption geometry of the intermediate and final states means that no rotation is required.

show abstract

Section: Resultssupporting

confidence: 89%

Ullmann Coupling Reactions on Ag(111) and Ag(110); Substrate Influence on the Formation of Covalently Coupled Products and Intermediate Metal-Organic Structures

Judd

Haddow

Champness

et al. 2017

Sci Rep

View full text Add to dashboard Cite

show abstract

“…Both products very much resemble the oligophenylene chains and hyperbenzene ( e. g . [18]‐honeycombene) rings produced from debrominated Ullmann reaction of DBTP on the same substrate …”

Section: Resultsmentioning

confidence: 99%

Dechlorinated Ullmann Coupling Reaction of Aryl Chlorides on Ag(111): A Combined STM and XPS Study

et al. 2019

Self Cite

View full text Add to dashboard Cite

Surface-assisted Ullmann coupling was widely applied to construct various molecular nanostructures on surfaces due to its reliability and controllability. By using 4,4''-dichloro-1,1':3',1''terphenyl (DCTP) as the precursor, covalently bonded zig-zag oligophenylene chains and hexagonal hyperbenzene rings, e. g., [18]-honeycombenes, were successfully fabricated on Ag(111) via dechlorinated Ullmann coupling reaction. Stepwise annealing was applied to investigate the reaction process in detail.Scanning tunneling microscopy and synchrotron X-ray photoemission spectroscopy were utilized to explore the thermal evolution of the DCTP molecules on Ag(111) under ultrahigh vacuum conditions, evidencing the existence of intact DCTP molecules, chemisorbed Cl atoms, covalently bonded DCTP dimers as well as organometallic CÀ AgÀ C-containing intermediates. These results may help understand dechlorinated Ullmann coupling reaction of aryl chlorides on metal surfaces.

show abstract

“…In on‐surface polymerizations, the product composition is additionally influenced by the two‐dimensional (2D) confinement and the specific interactions of the reactants with the surface. As a model reaction related to on‐surface synthesis of carbon‐based nanostructures, we study here the formation of azulene‐based organometallic oligo‐ and polymers from 1,3‐dibromoazulene (DBAz, Figure ). Such organometallic compounds of aromatic building blocks represent important and stable intermediates in the Ullmann‐type on‐surface synthesis of carbon‐based nanostructures .…”

Section: Introductionmentioning

confidence: 99%

The Macrocycle versus Chain Competition in On‐Surface Polymerization: Insights from Reactions of 1,3‐Dibromoazulene on Cu(111)

Krug¹,

Nieckarz

Fan³

et al. 2020

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Ring/chain competition in oligomerization reactions represents a long‐standing topic of synthetic chemistry and was treated extensively for solution reactions but is not well‐understood for the two‐dimensional confinement of surface reactions. Here, the kinetic and thermodynamic principles of ring/chain competition in on‐surface synthesis are addressed by scanning tunneling microscopy, X‐ray photoelectron spectroscopy, and Monte Carlo simulations applied to azulene‐based organometallic oligomers on Cu(111). Analysis of experiments and simulations reveals how the ring/chain ratio can be controlled through variation of coverage and temperature. At room temperature, non‐equilibrium conditions prevail and kinetic control leads to preferential formation of the entropically favored chains. In contrast, high‐temperature equilibrium conditions are associated with thermodynamic control, resulting in increased yields of the energetically favored rings. The optimum conditions for ring formation include the lowest possible temperature within the regime of thermodynamic control and a low coverage. The general implications are discussed and compared to the solution case.

show abstract

On-Surface Synthesis and Characterization of Honeycombene Oligophenylene Macrocycles

Cited by 39 publications

References 82 publications

Ullmann Coupling Reactions on Ag(111) and Ag(110); Substrate Influence on the Formation of Covalently Coupled Products and Intermediate Metal-Organic Structures

Ullmann Coupling Reactions on Ag(111) and Ag(110); Substrate Influence on the Formation of Covalently Coupled Products and Intermediate Metal-Organic Structures

Dechlorinated Ullmann Coupling Reaction of Aryl Chlorides on Ag(111): A Combined STM and XPS Study

The Macrocycle versus Chain Competition in On‐Surface Polymerization: Insights from Reactions of 1,3‐Dibromoazulene on Cu(111)

Contact Info

Product

Resources

About