Post‐Synthetic Decoupling of On‐Surface‐Synthesized Covalent Nanostructures from Ag(111)

Rastgoo‐Lahrood, Atena; Björk, Jonas; Lischka, Matthias; Eichhorn, Johanna; Kloft, Stephan; Fritton, Massimo; Strunskus, Thomas; Samanta, Debabrata; Schmittel, Michael; Heckl, Wolfgang M.; Lackinger, Markus

doi:10.1002/anie.201600684

Cited by 41 publications

(57 citation statements)

References 25 publications

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“…From the close‐up STM image (Figure b), we identify that the honeycomb structure is composed of well‐ordered elementary motifs as depicted by the white contours. As reported previously, I 2 would dissociate into atomic form and chemisorb on the surface under ultra high vacuum (UHV) conditions . According to the previous findings that halogen atoms are imaged as pronounced protrusions in STM images, we thus assign the bright spots indicated by the blue circles to iodine atoms.…”

Section: Methodssupporting

confidence: 58%

“…For on‐surface chemistry, iodine atoms usually act as byproducts of on‐surface dehalogenative reactions or can be trapped as guests in the self‐assembled structures . Very recently, the direct introduction of iodine onto metal surfaces under UHV conditions has been successfully achieved to decouple covalent networks from the surface as an intercalation . However, to our knowledge, the influence of halogen atoms on the formation of elementary metal–organic coordination motifs on surfaces has not been reported so far.…”

Section: Methodsmentioning

confidence: 99%

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Structural Transformation and Stabilization of Metal–Organic Motifs Induced by Halogen Doping

et al. 2017

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The structural transformation of supramolecular nanostructures with constitutional diversity and adaptability by dynamic coordination chemistry would be of fundamental importance for potential applications in molecular switching devices.T he role of halogen doping in the formation of elementary metal-organic motifs on surfaces has not been reported. Now,the 9-ethylguanine molecule (G) and Ni atom, as am odel system, are used for the structural transformation and stabilization of metal-organic motifs induced by iodine doping on Au(111). The iodine atoms are homogeneously located at particular hydrogen-richl ocations enclosed by G molecules by electrostatic interactions,which would be the key for such an unexpected stabilizing effect. The generality and robustness of this approach are demonstrated in different metal-organic systems (G/Fe) and also by chlorine and bromine.Scheme 1. Illustration of iodine-induced structuraltransformation and stabilization of elementary metal-organic motifs. Inset:chemical structure of the 9-ethylguanine molecule.

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Section: Methodssupporting

confidence: 58%

Section: Methodsmentioning

confidence: 99%

Structural Transformation and Stabilization of Metal–Organic Motifs Induced by Halogen Doping

et al. 2017

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“…From the close-up STM image (Figure 2b), we identify that the honeycomb structure is composed of well-ordered elementary motifs as depicted by the white contours.A s reported previously,I 2 would dissociate into atomic form and chemisorb on the surface under ultra high vacuum (UHV) conditions. [25] According to the previous findings [20,22,23] that halogen atoms are imaged as pronounced protrusions in STM images,w et hus assign the bright spots indicated by the blue circles to iodine atoms.M oreover,t he elementary motif also shows aprotrusion in the center which is naturally assigned to metal. According to the restraints of molecular geometry ensured by the ethyl groups,both N7 and O6 sites of Gm olecules should coordinate with metal atoms and only at hree-metal center could meet such ac riterion as reported in previous literatures.…”

Section: Angewandte Chemiementioning

confidence: 78%

Structural Transformation and Stabilization of Metal–Organic Motifs Induced by Halogen Doping

et al. 2017

View full text Add to dashboard Cite

The structural transformation of supramolecular nanostructures with constitutional diversity and adaptability by dynamic coordination chemistry would be of fundamental importance for potential applications in molecular switching devices. The role of halogen doping in the formation of elementary metal-organic motifs on surfaces has not been reported. Now, the 9-ethylguanine molecule (G) and Ni atom, as a model system, are used for the structural transformation and stabilization of metal-organic motifs induced by iodine doping on Au(111). The iodine atoms are homogeneously located at particular hydrogen-rich locations enclosed by G molecules by electrostatic interactions, which would be the key for such an unexpected stabilizing effect. The generality and robustness of this approach are demonstrated in different metal-organic systems (G/Fe) and also by chlorine and bromine.

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“…In a follow‐up study, Lackinger and his team used the high tendency of iodine atoms to form an iodine layer to post‐decouple on‐surface synthesized organic nanostructures from a silver surface . To this end, a submonolayer of a polyphenyl network was prepared via Ullmann‐type coupling on the Ag(111) surface.…”

Section: C−x Bond Activation—on‐surface Ullmann‐type Couplingmentioning

confidence: 99%

Covalent‐Bond Formation via On‐Surface Chemistry

Held

Fuchs

Studer

2017

Chemistry A European J

141

133

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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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Post‐Synthetic Decoupling of On‐Surface‐Synthesized Covalent Nanostructures from Ag(111)

Cited by 41 publications

References 25 publications

Structural Transformation and Stabilization of Metal–Organic Motifs Induced by Halogen Doping

Structural Transformation and Stabilization of Metal–Organic Motifs Induced by Halogen Doping

Structural Transformation and Stabilization of Metal–Organic Motifs Induced by Halogen Doping

Covalent‐Bond Formation via On‐Surface Chemistry

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