Surface mediated synthesis of 2D covalent organic frameworks: 1,3,5-tris(4-bromophenyl)benzene on graphite(001), Cu(111), and Ag(110)

Gutzler, Rico; Walch, Hermann; Eder, Georg; Kloft, Stephan; Heckl, Wolfgang M.; Lackinger, Markus

doi:10.1039/b906836h

Cited by 314 publications

(366 citation statements)

References 21 publications

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“…As was the case with TIPT, the structure of Figure 4a is different from that reported in the literature for the analogous molecule TBPB on HOPG, which features an oblique unit cell. 41 It is interesting to note that TIPT and TBPT networks on HOPG have same u vector despite the different size of the halogen atoms, which in turn leads to different v vectors and trimeric angles θ (for TBPT θ = 129 ± 6°, see Table 1). This may arise from a commensurability effect between the SAMNs and the substrate, which would also explain the discrepancies between the experimental and DFTcomputed molecular unit cells (Figure 1b and Figure 4).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The packing differs from that reported in the literature for similar molecules TIPB and TBPB on HOPG. 41,46,49 This is attributed to stronger molecule···substrate interactions due to the presence of the triazine core, which makes TIPT and TBPT stiffer and planar precursors. Varying the solvents revealed that TBPT can form a bicomponent polymorph involving a hexameric R 6 6 (24) hydrogen-bonded arrangement of the solvent (heptanoic acid) molecules.…”

Section: ■ Conclusion and Perspectivesmentioning

confidence: 99%

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Substrate, Molecular Structure, and Solvent Effects in 2D Self-Assembly via Hydrogen and Halogen Bonding

et al. 2014

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Recently, halogen···halogen interactions have been demonstrated to stabilize two-dimensional supramolecular assemblies at the liquid−solid interface. Here we study the effect of changing the halogen, and report on the 2D supramolecular structures obtained by the adsorption of 2,4,6-tris(4-bromophenyl)-1,3,5-triazine (TBPT) and 2,4,6-tris(4-iodophenyl)-1,3,5-triazine (TIPT) on both highly oriented pyrolytic graphite and the (111) facet of a gold single crystal. These molecular systems were investigated by combining room-temperature scanning tunneling microscopy in ambient conditions with density functional theory, and are compared to results reported in the literature for the similar molecules 1,3,5-tri(4-bromophenyl)benzene (TBPB) and 1,3,5-tri(4-iodophenyl)benzene (TIPB). We find that the substrate exerts a much stronger effect than the nature of the halogen atoms in the molecular building blocks. Our results indicate that the triazine core, which renders TBPT and TIPT stiff and planar, leads to stronger adsorption energies and hence structures that are different from those found for TBPB and TIPB. On the reconstructed Au(111) surface we find that the TBPT network is sensitive to the fcc-and hcp-stacked regions, indicating a significant substrate effect. This makes TBPT the first molecule reported to form a continuous monolayer at room temperature in which molecular packing is altered on the differently reconstructed regions of the Au(111) surface. Solvent-dependent polymorphs with solvent coadsorption were observed for TBPT on HOPG. This is the first example of a multicomponent self-assembled molecular networks involving the rare cyclic, hydrogen-bonded hexamer of carboxylic groups, R 6 6 (24) synthon.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Conclusion and Perspectivesmentioning

confidence: 99%

Substrate, Molecular Structure, and Solvent Effects in 2D Self-Assembly via Hydrogen and Halogen Bonding

et al. 2014

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“…15,[36][37][38] This leads in general to a second reaction step, the intermolecular Ullmann carbon-carbon coupling. 15,16,22,36,[39][40][41][42][43][44][45] Here, our initial aim was to utilize an on-surface chemical reaction to produce covalently bonded linear polymers. In order to characterize the structure of the unreacted monomer units, the I 2 TMTP molecule was deposited onto an Au(111) sample held at a temperature of approximately 30K with the C-I bond expected to remain intact upon molecular adsorption, due to the low temperature.…”

Section: Resultsmentioning

confidence: 99%

Manipulating the Conformation of Single Organometallic Chains on Au(111)

et al. 2013

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The conformations of organometallic polymers formed via the bottom-up assembly of monomer units on a metal surface are investigated, and the relationship between the adsorption geometry of the individual monomer units, the conformational structure of the chain, and the overall shape of the polymer is explored. Iodine-functionalized monomer units deposited onto a Au (111) substrate are found to form linear chain structures, where each monomer is linked to its neighbors via an Au adatom. Lateral manipulation of the linear chains using a scanning tunneling microscope allows the structure of the chain to be converted from a linear geometry to a curved one, and it is shown that a transformation of the overall shape of the chain is coupled to a conformational re-arrangement of the chain structure as well as a change in the adsorption geometry of the monomer units within the chain. The observed conformational structure of the curved chain is well ordered and distinct from that of the linear chains. The structures of both the linear and curved chains are investigated by a combination of scanning tunneling microscopy measurements and theoretical calculations.

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“…Thus, it is a timely issue to explore acetylenic coupling at interfaces, and recent studies using a sequential protocol with monolayer self-assembly followed by a crosslinking step provided encouraging results 11 . Pursuing a different vein, there is the prospective research domain dealing with on-surface covalent reactions under ultrahigh vacuum (UHV) conditions on clean metal surfaces to realize novel functional nano-architectures and networks [12][13][14][15][16][17][18][19] . However, many of the employed protocols imply appreciable activation barriers or rely on the enabling character of a set of leaving groups.…”

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confidence: 99%

Homo-coupling of terminal alkynes on a noble metal surface

et al. 2012

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The covalent linking of acetylenes presents an important route for the fabrication of novel carbon-based scaffolds and two-dimensional materials distinct from graphene. To date few attempts have been reported to implement this strategy at well-defined interfaces or monolayer templates. Here we demonstrate through real space direct visualization and manipulation in combination with X-ray photoelectron spectroscopy and density functional theory calculations the Ag surface-mediated terminal alkyne C sp À H bond activation and concomitant homo-coupling in a process formally reminiscent of the classical Glaser-Hay type reaction. The alkyne homo-coupling takes place on the Ag(111) noble metal surface in ultrahigh vacuum under soft conditions in the absence of conventionally used transition metal catalysts and with volatile H 2 as the only by-product. With the employed multitopic ethynyl species, we demonstrate a hierarchic reaction pathway that affords discrete compounds or polymeric networks featuring a conjugated backbone. This presents a new approach towards on-surface covalent chemistry and the realization of two-dimensional carbon-rich or allcarbon polymers.

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Surface mediated synthesis of 2D covalent organic frameworks: 1,3,5-tris(4-bromophenyl)benzene on graphite(001), Cu(111), and Ag(110)

Abstract: The on surface synthesis of a two-dimensional (2D) covalent organic framework from a halogenated aromatic monomer under ultra-high vacuum conditions is shown to be dependent on the choice of substrate.

Cited by 314 publications

References 21 publications

Substrate, Molecular Structure, and Solvent Effects in 2D Self-Assembly via Hydrogen and Halogen Bonding

Substrate, Molecular Structure, and Solvent Effects in 2D Self-Assembly via Hydrogen and Halogen Bonding

Manipulating the Conformation of Single Organometallic Chains on Au(111)

Homo-coupling of terminal alkynes on a noble metal surface

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