Surface-Assisted Assembly of Discrete Porphyrin-Based Cyclic Supramolecules

Heim, Daniel; Seufert, Knud; Auwärter, Willi; Aurisicchio, Claudia; Fabbro, Chiara; Bonifazi, Davide; Barth, Johannes V.

doi:10.1021/nl9029994

Cited by 97 publications

(102 citation statements)

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“…We need to consider that the dimer formation proceeds under conditions where substrate step fluctuations occur and silver adatoms exist on the surface. This might interfere with the surface-assisted reaction and potentially afford organometallic Ag bis-acetylide complexes, similar to related scenarios on Cu surfaces [26][27][28] . The covalently bonded dimer was relaxed on the Ag(111) surface and an STM image simulation was carried out with the equilibrium structure ( Fig.…”

Section: Resultsmentioning

confidence: 71%

“…The inset shows a magnified image of the associated honeycomb unit, and a corresponding HYPERCHEM model that nicely fits the STM data. By contrast, the additional five-and seven-fold cyclic structures imply distortions of the molecular modules 27,28,35 . In addition, some features are visible where three molecular terminations join together, which can be of different origin including covalent connexions differing from the intended butadiyne bridges as further discussed in the Supplementary Information (Supplementary Fig.…”

Section: Resultsmentioning

confidence: 97%

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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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Section: Resultsmentioning

confidence: 71%

Section: Resultsmentioning

confidence: 97%

Homo-coupling of terminal alkynes on a noble metal surface

et al. 2012

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“…Moreover, porphyrins adsorbed at metal surfaces offer a rich playground for the exploration of model interfacial coordination systems. [17][18][19][20][21] To this end it is of crucial importance to cope with their electronic properties [22][23][24] and inherent conformational flexibility, which can interfere in supramolecular organization 25,26 and allow for unconvential ligation modes of adducts 27,28 .…”

Section: Introductionmentioning

confidence: 99%

Self-metalation of 2H-tetraphenylporphyrin on Cu(111): An x-ray spectroscopy study

Diller

Klappenberger

Marschall

et al. 2012

The Journal of Chemical Physics

162

319

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The bonding and the temperature-driven metalation of 2H-Tetraphenylporphyrin (2H-TPP) on the Cu(111) surface under ultrahigh vacuum (UHV) conditions were investigated by a combination of X-ray photoelectron spectroscopy (XPS) and nearedge X-ray absorption fine structure (NEXAFS) spectroscopy with density functional theory (DFT) calculations. Thin films were prepared by organic molecular beam epitaxy and subsequent annealing. Our systematic study provides an understanding of the changes of the spectroscopic signature during adsorption and metalation. Specifically, we achieved a detailed peak assignment of the 2H-TPP multilayer data of

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“…[1][2][3] The construction of desired molecular network architectures on suitable substrates is achieved by the self-assembly of molecular building blocks, which is mainly controlled by a complex interplay between non-covalent bonds such as hydrogen bonds, van der Waals and electrostatic interactions, and the epitaxy on the substrate. [4][5][6][7][8][9][10][11][12][13][14] From the knowledge gained about the delicate balance between intermolecular and molecule-substrate interactions, the functional nano-networks can then be tuned by adjusting functional groups of the molecule to gain the desired architectures [15][16][17] and the interface electronic structure for the specific application. Therefore, it is important that the molecular orientation, configuration and conformation, and the interactions between the adsorbed molecules and the substrate as well as between molecules can be identified and understood, e.g.…”

Section: Introductionmentioning

confidence: 99%

Interplay of hydrogen bonding and molecule–substrate interaction in self-assembled adlayer structures of a hydroxyphenyl-substituted porphyrin

et al. 2014

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The formation of hydrogen-bonded organic nano-structures and the role of the substrate lattice thereby were investigated by scanning tunneling microscopy. The self-organization of 5,10,15,20-tetra(p-hydroxyphenyl)porphyrin (H 2 THPP) molecules leads to two molecular arrangements on Au(111). One of these is characterized by pair-wise hydrogen bonding between hydroxyl groups and a low packing density which enables a rotation of individual molecules in the structure. A different interaction with stronger chain-like hydrogen bonding and additional interactions of phenyl groups was observed for the second structure. The influence of the substrate on the epitaxial behavior is demonstrated by the adsorption of H 2 THPP on the highly anisotropic Ag(110) substrate. There, several balances between the occupation of favorable adsorption positions and the number of hydrogen bonds per molecule were found. The molecules form molecular chains on Ag(110) and also assemble into two-dimensional periodic arrangements of differently sized close-packed blocks similar to the second type of supramolecular ordering found on Au(111). Dispersion corrected Density Functional Theory calculations were applied to understand the adsorption and complex epitaxy of these molecules. It is shown that the azimuthal orientation of the saddle-shape deformed molecule plays an important role not only for the intermolecular but also for the molecule-substrate interaction.

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Surface-Assisted Assembly of Discrete Porphyrin-Based Cyclic Supramolecules

Cited by 97 publications

References 50 publications

Homo-coupling of terminal alkynes on a noble metal surface

Homo-coupling of terminal alkynes on a noble metal surface

Self-metalation of 2H-tetraphenylporphyrin on Cu(111): An x-ray spectroscopy study

Interplay of hydrogen bonding and molecule–substrate interaction in self-assembled adlayer structures of a hydroxyphenyl-substituted porphyrin

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