Quinone-Facilitated Coordinated Bipyrene and Polypyrene on Au(111) by Capture of Gold Adatoms

Abstract

Precise “bottom-up” synthesis by surface-assisted chemical reaction provides advanced approaches for the fabrication of two-dimensional (2D) robust covalent nanostructures, which are bound to contain defects due to the irreversible properties of covalent bonds. The further introduction of metal–organic coordination interactions possessing self-correction abilities and yielding comparable stabilities would be a strategically advanced supplement for the construction of well-ordered complex covalent networks. In this report, the on-surface synthesis of Au-coordinated bipyrenes and polypyrenes is achieved on Au(111) by a combination of triggering surface-assisted dehalogenative coupling and capture of Au adatoms. The resulting nanostructures are characterized using a scanning tunneling microscope and X-ray photoelectron spectroscopy analysis and further verified by density functional theory calculations. Quinone group functionality present in the pyrene precursor molecules is the key by which the formation of O–Au–O coordination bonds is facilitated, in turn forcing the expulsion of bromine atoms from the thus formed 2D nanostructures.

Surface-assisted fabrication of low-dimensional carbon-based nanoarchitectures

“…Br sitting atop the Au adatoms in OM species [164]. Through modifying Br 2 Py with ketone group, the resultant covalent chains based on surface Ullmann coupling displayed coordination to Au adatoms on Au (111) [165]. Afterwards, they investigated the Ullman coupling of same molecule on Ag (111) [166] and semi-metallic Bi(111)/Ag (111) [167].…”

Structural Transformation of Azonia[5]helicene Photoproduct via Reaction Field Function of Layered Inorganic Material

“…This research area is called “on surface synthesis.” Chemical reactions have been carried out on flat metallic surfaces, such as Au (111) and Cu (001). The reaction products can be observed directly by imaging the molecular structure using scanning tunneling microscopy (STM) and atomic force microscopy (AFM). − This direct observation is one of the clear advantages of this field, but the interesting point of this system is the shape of the reaction field. Interactions between flat metallic surfaces and organic molecules accelerate chemical reactions and sometimes transform the molecular structure of the final product into a more planar structure. ,− Flat reaction fields have unique potential in organic chemistry because they can exert novel steric effects on molecules that do not appear in solution systems.…”

Self-assembly and spectroscopic fingerprints of photoactive pyrenyl tectons on hBN/Cu(111)

“…With prominent fluorescence properties, pyrene is often considered the "fruitfly of photochemists", and several materials have been prepared for applications in optoelectronic devices and organic electronics [47]. On metal surfaces under ultrahigh vacuum (UHV), unsubstituted [55] as well as functionalized pyrene de-rivatives [9,48,[56][57][58][59][60][61][62][63][64] were employed as versatile tectons to engineer supramolecular [9,48,[55][56][57][58][59][61][62][63][64] and covalent architectures [56,[58][59][60]64]. On two-dimensional materials, pyrene serves as an anchor for noncovalent functionalization, e.g., to develop graphene platforms to be used in sensing applications [65][66][67] and to employ hBN monolayers for capturing aromatic organic pollutants [68].…”