Protecting‐Group‐Controlled Surface Chemistry—Organization and Heat‐Induced Coupling of 4,4′‐Di(<i>tert</i>‐butoxycarbonylamino)biphenyl on Metal Surfaces

Boz, Serpil; Stöhr, Meike; Soydaner, Umut; Mayor, Marcel

doi:10.1002/anie.200804845

Cited by 31 publications

(22 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Stöhr and Mayor reported an interesting observation concerning the reaction behavior of tert ‐butoxycarbonyl‐protected (Boc‐protected) arylamines on a Cu(111) surface . After annealing of a submonolayer of Boc‐protected 4,4′‐diaminobiphenyl to a temperature of 196 °C, formation of linear dimers connected via an azo linkage was observed (Figure a).…”

Section: Other Chemical Functionalities In On‐surface Reactionsmentioning

confidence: 95%

See 1 more Smart Citation

Covalent‐Bond Formation via On‐Surface Chemistry

Held

Fuchs

Studer

2017

Chemistry A European J

146

134

View full text Add to dashboard Cite

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.

show abstract

Section: Other Chemical Functionalities In On‐surface Reactionsmentioning

confidence: 95%

“… On‐surface reactions of a) BOC‐protected aryl amines, b) isocyanate and amines and c) trans ‐(NH 2 ) 2 TPP . (Adapted with permission from ref.…”

Section: Other Chemical Functionalities In On‐surface Reactionsmentioning

confidence: 99%

Covalent‐Bond Formation via On‐Surface Chemistry

Held

Fuchs

Studer

2017

Chemistry A European J

146

134

View full text Add to dashboard Cite

show abstract

“…It has already been shown, that a transformation of a urea derivative to an azo compound on silver surface under high vacuum conditions and at high temperatures is possible. [317] This reaction which occurred on single molecules adsorbed on a silver surface under reduced pressure was mimicked as a wet chemistry reaction. Since macrocycle 120 needed to be synthesized in a larger scale, surface chemistry is not practicable.…”

Section: Synthesis Of the Triflate Functionalized Biphenylmentioning

confidence: 99%

Shape‐Switchable Azo‐Macrocycles

et al. 2009

Self Cite

View full text Add to dashboard Cite

The synthesis of four shape‐switchable macrocycles comprising different peripheral substituents is described. The macrocycles 1–4 consist of m‐terphenyl semicircles interlinked by two azo joints. These macrocycles were assembled from nitro‐functionalized m‐terphenyl moieties through reductive dimerization. The semicircles were assembled through Suzuki cross‐coupling reactions. The molecular weights of the macrocycles were determined by vapour pressure osmometry, because mass spectrometry failed in the cases of 2 and 3. The E → Z photoisomerization reactions were analysed by UV/Vis spectroscopy complemented by 1H NMR studies. A very slow thermal back‐reaction indicated considerable stabilization of the Z isomer. The reduced efficiency of the thermal back‐reaction probably arises from the reduced degree of freedom due to the mechanical interlinking of the two azo groups. The photostationary state consisted of all‐Z (85 %) and all‐E isomers (15 %). The E → Z transformation induced by irradiation displayed simple exponential kinetics, which indicates pairwise switching of the two azo groups in a macrocycle, at least on the timescale under investigation. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

show abstract

“…The arrangement of the P3 molecules is similar to the herringbone structure of 4,4′-di(tert-butoxycarbonylamino)biphenyl molecules. 56 A unit cell is outlined with the parameters of a = 1.7 ± 0.1 nm, b = 1.3 ± 0.1 nm, and θ = 85 ± 3°, as indicated by the FFT image (inset in Figure 3a). …”

Section: Resultsmentioning

confidence: 99%

Proton-Assisted Self-Assemblies of Linear Di-Pyridyl Polyaromatic Molecules at Solid/Liquid Interface

Shang

et al. 2012

J. Phys. Chem. C

View full text Add to dashboard Cite

Proton-assisted self-assemblies of three linear dipyridyl polyaromatic molecules, namely, 4,4′-bipyridine, 1,4-di(4-pyridyl)-benzene, and 4,4′-di(4-pyridyl)biphenyl, at the heptanoic acid/highly oriented pyrolytic graphite interface were systematically studied with scanning tunneling microscopy. A major finding was that protons from strong acids could greatly accelerate the assembling processes of 4,4′-bipyridine and 1,4-di(4-pyridyl)benzene molecules and, in the case of 4,4′-di(4-pyridyl)biphenyl molecule, lead to structural transformation in the self-assembling process in analogy to the role of a catalyst in a catalytic process. The experimental results could be rationalized by a simple mechanism involving protonassisted formation of intermolecular hydrogen bonds, which provides new insights with regards to the self-assembling processes in solutions, especially under acidic bioenvironments.

show abstract

Protecting‐Group‐Controlled Surface Chemistry—Organization and Heat‐Induced Coupling of 4,4′‐Di(tert‐butoxycarbonylamino)biphenyl on Metal Surfaces

Abstract: Like pearls on a string, molecular building blocks have been preorganized and then interlinked on a surface (see STM images). In this way both the supramolecular self‐assembly of the reactants as well as the subsequent thermal activation to release the protecting group are controlled.

Cited by 31 publications

References 32 publications

Covalent‐Bond Formation via On‐Surface Chemistry

Covalent‐Bond Formation via On‐Surface Chemistry

Shape‐Switchable Azo‐Macrocycles

Proton-Assisted Self-Assemblies of Linear Di-Pyridyl Polyaromatic Molecules at Solid/Liquid Interface

Contact Info

Product

Resources

About