Cyclotrimerization‐Induced Chiral Supramolecular Structures of 4‐Ethynyltriphenylamine on Au(111) Surface

Xiang, Feifei; Lü, Yan; Li, Chao; Song, Xin; Liu, Xiaoqing; Wang, Zhongping; Liu, Juan; Dong, Mingdong; Wang, Li

doi:10.1002/chem.201501434

Cited by 17 publications

(11 citation statements)

References 61 publications

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“…An early example of an on‐surface cyclization is the cyclotrimerization of terminal aryl alkynes, which was initially discovered as a side reaction in the on‐surface Glaser coupling (see discussion above). While initially regarded as an undesirable reaction path, in follow‐up studies on‐surface reactivity of aryl alkynes was optimized towards trimerization to generate two‐dimensional hexagonal structures at the surface containing benzene branching units . This was convincingly demonstrated by Müllen and Fasel for the preparation of well‐ordered, two‐dimensional network structures on a gold surface .…”

Section: On‐surface Cycloadditions and Cyclization Reactionsmentioning

confidence: 99%

Covalent‐Bond Formation via On‐Surface Chemistry

Held

Fuchs

Studer

2017

Chemistry A European J

146

134

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In this Review article pioneering work and recent achievements in the emerging research area of on-surface chemistry is discussed. On-surface chemistry, sometimes also called two-dimensional chemistry, shows great potential for bottom-up preparation of defined nanostructures. In contrast to traditional organic synthesis, where reactions are generally conducted in well-defined reaction flasks in solution, on-surface chemistry is performed in the cavity of a scanning probe microscope on a metal crystal under ultrahigh vacuum conditions. The metal first acts as a platform for self-assembly of the organic building blocks and in many cases it also acts as a catalyst for the given chemical transformation. Products and hence success of the reaction are directly analyzed by scanning probe microscopy. This Review provides a general overview of this chemistry highlighting advantages and disadvantages as compared to traditional reaction setups. The second part of the Review then focuses on reactions that have been successfully conducted as on-surface processes. On-surface Ullmann and Glaser couplings are addressed. In addition, cyclodehydrogenation reactions and cycloadditions are discussed and reactions involving the carbonyl functionality are highlighted. Finally, the first examples of sequential on-surface chemistry are considered in which two different functionalities are chemoselectively addressed. The Review gives an overview for experts working in the area but also offers a starting point to non-experts to enter into this exciting new interdisciplinary research field.

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Section: On‐surface Cycloadditions and Cyclization Reactionsmentioning

confidence: 99%

Covalent‐Bond Formation via On‐Surface Chemistry

Held

Fuchs

Studer

2017

Chemistry A European J

146

134

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“…These surfaces would induce different conformational strains with enantiomers and thus exhibit distinct adsorption capability [22, 23] . The in situ observations based on scanning tunneling microscopy also proved the interactions between amino acids and metals may induce the chiral packing on the metal surfaces [24, 25] . These results suggest that chiral metal surfaces may act as a new potential platform for constructing novel chiral sensors, which possess the capability of both chiral detection and separation.…”

Section: Introductionmentioning

confidence: 80%

Chiral Recognition on Bare Gold Surfaces by Quartz Crystal Microbalance

et al. 2021

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Quartz crystal microbalance (QCM) is one of the powerful tools for the studies of molecular recognition and chiral discrimination. Its efficiency mainly relies on the design of the functional sensitive layer on the electrode surface. However, the organic sensitive layer may easily cause dissipation of oscillation or detachment and weaken the signal transfer during the molecular recognition processes. In this work, we reveal for the first time that the bare metal surface without the organic selector layer has the capability for chiral recognition in the QCM system. During the adsorption of various chiral amino acids, relatively higher selectivity of D‐enantiomers on gold (Au) surface was shown by the QCM detection. Based on analyses of the surface crystalline structure and density functional theory calculations, we demonstrate that the chiral nature of Au surface plays an important role in the selective binding of specific D‐amino acids. These results may open new insights on chiral detection by QCM system. It will also promote the construction of novel chiral sensing systems with both efficient detection and separation capability.

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“…We rather postulate an activated oligomerization via strong bond formation which is supported by the fact that the trimers are impossible to separate by STM‐tip induced manipulation. The likeliest mechanisms are either a [2+2+2] cyclization of alkynes, which has been reported for different molecules on Au(111) and Cu(111), or a coordination to individual Pd or Ga surface adatoms or to carbon‐based fragments. The [2+2+2] cyclization as formation mechanism of the 9‐EP propellers can be excluded due to the excessively large spatial separation of the phenanthrene moieties (Figure S7).…”

Section: Figurementioning

confidence: 97%

Near‐Enantiopure Trimerization of 9‐Ethynylphenanthrene on a Chiral Metal Surface

et al. 2020

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Enantioselectivity in heterogeneous catalysis strongly depends on the chirality transfer between catalyst surface and all reactants, intermediates, and the product along the reaction pathway. Herein we report the first enantioselective on‐surface synthesis of molecular structures from an initial racemic mixture and without the need of enantiopure modifier molecules. The reaction consists of a trimerization via an unidentified bonding motif of prochiral 9‐ethynylphenanthrene (9‐EP) upon annealing to 500 K on the chiral Pd3‐terminated PdGa{111} surfaces into essentially enantiopure, homochiral 9‐EP propellers. The observed behavior strongly contrasts the reaction of 9‐EP on the chiral Pd1‐terminated PdGa{111} surfaces, where 9‐EP monomers that are in nearly enantiopure configuration, dimerize without enantiomeric excess. Our findings demonstrate strong chiral recognition and a significant ensemble effect in the PdGa system, hence highlighting the huge potential of chiral intermetallic compounds for enantioselective synthesis and underlining the importance to control the catalytically active sites at the atomic level.

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Cyclotrimerization‐Induced Chiral Supramolecular Structures of 4‐Ethynyltriphenylamine on Au(111) Surface

Cited by 17 publications

References 61 publications

Covalent‐Bond Formation via On‐Surface Chemistry

Covalent‐Bond Formation via On‐Surface Chemistry

Chiral Recognition on Bare Gold Surfaces by Quartz Crystal Microbalance

Near‐Enantiopure Trimerization of 9‐Ethynylphenanthrene on a Chiral Metal Surface

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